Unsymmetrical Ligand Electrochemical Oxidation of a Cu(II ...1 Supporting Information Elucidating...
Transcript of Unsymmetrical Ligand Electrochemical Oxidation of a Cu(II ...1 Supporting Information Elucidating...
1
Supporting Information
Elucidating the Secondary Effect in Lewis Acid Mediated Anodic Shift of Electrochemical Oxidation of a Cu(II) Complex with N2O2 Donor Unsymmetrical Ligand
Souvik Maitydagger Soumavo Ghoshdagger and Ashutosh Ghoshdagger
daggerDepartment of Chemistry University College of Science University of Calcutta 92 A P C
Road Kolkata 700009 India Email ghosh_59yahoocom (AG) sanjuchem08gmailcom
(SG)
Fig S1 BenesiminusHilderbrand plot for [CuL] + K+ (upper panel left side) [CuL] + Na+ (upper
panel right side) [CuL] + Mg2+ (lower panel left side) and [CuL] + Ca2+ (lower panel right side)
complex formation
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2019
2
Fig S2 BenesiminusHilderbrand plot for [CuL] + Li+ (upper panel) [CuL] + Zn2+ (lower panel left
side) and [CuL] + Cd2+ (lower panel right side) complex formation
3
Fig S3 Representative ESI mass spectrum of [CuL]ndashLi+ mixture in acetonitrile
Fig S4 Representative ESI mass spectrum of [CuL]ndashZn2+ mixture in acetonitrile
4
Fig S5 Representative ESI mass spectrum of [CuL]ndashCd2+ mixture in acetonitrile
Fig S6 Representative ESI mass spectrum of [CuL]ndashPr3+ mixture in acetonitrile
5
Fig S7 Representative ESI mass spectrum of [CuL]ndashNd3+ mixture in acetonitrile
Fig S8 Representative ESI mass spectrum of [CuL]ndashSm3+ mixture in acetonitrile
6
Fig S9 Dependence of LMCT energy bands on pKa of M(aqua)n+ ion as a measure of its Lewis acidity in presence of 100 equivalent of MprimeXn salts
Fig S10 Potential scan of unbound [CuL] and [CuL]+K+ upto first oxidation step
7
Fig S11 Left Multicycle CV of [CuL] Right CV of [CuL] at different concentration at 300 mVS scan rate in acetonitrile
Fig S12 Differential pulse voltametric (DPV) analysis of unbound [CuL] and [CuL]+K+
8
Fig S13 Cyclic voltammograms of electrochemical reduction of unbound [CuL] (upper panel
left side) and [CuL] + 10 equiv of KPF6 (upper panel right side) in acetonitrile at multiple scan
rate (mVS-1) and Differential pulse voltametric (DPV) analysis of unbound [CuL] and
[CuL]+K+(lower panel) at a scan rate of 20 mVS-1
9
Fig S14 Left Panel Cyclic voltammograms of Cu(III) couple in presence of 10 equiv of
specified redox-inactive metal ions in acetonitrile at a scan rate of 300 mVs-1 Right panel DPV
analysis of the corresponding mixtures at a scan rate of 20 mVs-1
10
Fig S15 Top UV-VIS spectra Middle CV (300 mVs-1 scan rate) and Bottom DPV (20 mVs-1 scan rate) of complex 1 at different potential range in presence of 100 equiv of TBAHFP in acetonitrile
11
Fig S16 Top UV-VIS spectra Middle CV (300 mVs-1 scan rate) and Bottom DPV (20 mVs-1 scan rate) of complex 2 at different potential range in presence of 100 equiv of TBAHFP in acetonitrile
12
Fig S17 Dependence of half-wave potentials (E12) of electrochemical reduction of the
heterometallic complexes ([(CuL)M]n+) vs pKa of M(aqua)n+ ions as measure of their Lewis
acidity
Fig S18 Electrochemical response of [CuL] in acetonitrile upon incremental addition of aquous
acetonirile (left) and the corresponding change in molar extinction coefficient of LMCT band
(right)
13
Fig S19 Electrochemical response of [CuL] + 10 eqv Zn2+ in acetonitrile upon incremental
addition of aquous acetonirile (left) and the corresponding change in molar extinction coefficient
of LMCT band (right)
Fig S20 Electrochemical response of [CuL] + 10 eqv Mg2+ in acetonitrile upon incremental
addition of aquous acetonirile (left) and the corresponding change in molar extinction coefficient
of LMCT band (right)
14
Fig S21 Correlation of shift of oxidation peak potential with equivalent of water added for
[CuL]+Mn+( Mn+ = Pr3+ Zn2+ Mg2+) (Solid line is guide for eye)
Fig S22 Correlation of change of molar absorptivity with equivalent of water added for
[CuL]+Mn+( Mn+ = Pr3+ Zn2+ Mg2+) (Solid line is guide for eye)
15
Fig S23 Correlation of the shift of oxidation peak potential with the change of molar extinction
coefficient of [CuL] in acetonitrile upon incremental addition of aquous acetonirile
Fig S24 Correlation of the shift of oxidation peak potential with the change of molar extinction
coefficient of [CuL]+10 eqv Zn2+ in acetonitrile upon incremental addition of aquous
acetonirile
16
Fig S25 Correlation of the shift of oxidation peak potential with the change of molar extinction
coefficient of [CuL]+10 eqv Mg2+ in acetonitrile upon incremental addition of aquous
acetonirile
Table S1 List of bond lengths (Aring) and bond angles (ordm) of complexes 1 and 2
M = K M = Zn
M(1)O(1) 2020(6) 2000(4)
M(1)O(2) 2179(5) 2279(5)
M(1)O(3) 2012(5) 1986(4)
M(1)O(4) 2184(6)) 2345(5)
M(1)O(5) 2058(6) 2062(5)
M(1)O(6) 2037(5) 2031(5)
Cu(1)O(1) 1920(5) 1909(5)
Cu(1)O(2) 1944(4) 1917(4)
Cu(1)N(1) 2004(6) 1982(6)
Cu(1)N(2) 1937(7) 1913(6)
Cu(2)O(3) 1909(5) 1922(5)
17
Cu(2)O(4) 1937(5) 1896(4)
Cu(2)N(3) 1966(5) 1963(5)
Cu(2)N(4) 1933(7) 1927(5)
O(1)M(1)O(2) 7448(18) 7182(17)
O(1)M(1)O(3) 1567(2) 14831(19)
O(1)M(1)O(4) 891(2) 8456(17)
O(1)M(1)O(5) 1020(2) 1061(2)
O(1)M(1)O(6) 942(2) 954(2)
O(2)M(1)O(3) 8738(19) 8400(18)
O(2)M(1)O(4) 813(2) 7719(17)
O(2)M(1)O(5) 929(2) 9441(18)
O(2)M(1)O(6) 1684(2) 16616(18)
O(3)M(1)O(4) 734(2) 7002(16)
O(3)M(1)O(5) 933(2) 9563(19)
O(3)M(1)O(6) 1028(2) 1058(2)
O(4)M(1)O(5) 1657(2) 16385(18)
O(4)M(1)O(6) 963(2) 9675(18)
O(5)M(1)O(6) 919(2) 943(2)
O(1)Cu(1)O(2) 824(2) 8238(18)
O(1)Cu(1)N(1) 905(2) 902(2)
O(1)Cu(1)N(2) 1693(3) 1690(2)
O(2)Cu(1)N(1) 1633(2) 1656(2)
O(2)Cu(1)N(2) 918(3) 920(2)
N(1)Cu(1)N(2) 974(3) 973(2)
O(2)Cu(2)O(3) 7047(16) 6993(16)
O(2)Cu(2)O(4) 684(2) 7092(17)
O(2)Cu(2)N(3) 982(2) 9683(17)
O(2)Cu(2)N(4) 1134(2) 11492(18)
18
O(3)Cu(2)O(4) 815(2) 8190(18)
O(3)Cu(2)N(3) 903(2) 901(2)
O(3)Cu(2)N(4) 1712(2) 1717(2)
O(4)Cu(2)N(3) 1660(3) 1671(2)
O(4)Cu(2)N(4) 925(3) 932(2)
N(3)Cu(2)N(4) 968(3) 959(2)
Table S2 Correlation of electrochemical response of previously reported 11 metallohost redox-inactive ion adducts derived from bicompartmental macrocyclic ligands containing adjacent N2O2 and 18-crown-6 like cavity with pKa of corresponding metal-aqua complex
[MnL](PF6)+MXn in acetonitrile MXn =
pKa E12 for Mn(IIIII) (V vs SCE)
KPF6 1625 0025LiClO4 1382 0055Ba(OTf)2 1336 0200Ca(OTf)2 1260 0245
Li+(expected)
[Li+(experimental) - Li+(expected)]
0176
0055 - 0176 =-0121
Data plotted from reference [16] of the main text
[NiL]+MXn in acetonitrileMXn =
pKa EPC for Ni(III)(V vs ferrocene)
NaPF6 1477 -165Ca(OTf)2 1260 -142Nd(OTf)3 843a -118Y(OTf)3 804a -122
Y3+(expected)
[Y3+(experimental) - Y3+(expected)]
-113
-122-(-113) =-009
aobtained from ref Data plotted from reference [17] of the main text
19
[56] of main text[CoL] + MXn in DMF MXn =
pKa E12 for Co(III)(V vs ferrocene)
K(OTf) 1625 -158Na(OTf) 1477 -158Ba(OTf)2 1336 -148Sr(OTf)2 1318 -144Ca(OTf)2 1260 -141
Na+(expected)
[Na+(experimental) - Na+(expected)]
-1515
-158 - (-1515)=-0065
Data plotted from reference [18] of the main text
[CuL]+Mn+ in DMSO Mn+=
pKa E12 for Cu(III)(V vs AgAgCl)
K+ 1625 -1277Na+ 1477 -1279Li+ 1382 -1286Ba2+ 1336 -1119Na+(expected)
[Na+(experimental) - Na+(expected)]
Li+(expected)
[Li+(experimental) - Li+(expected)]
-1185-1279-(-1185)=-0094
-1134-1286-(-1134)=-0152
Data plotted from reference [19] of the main text Line is guide for eye
[Mn(N)L] + MXn in acetonitrile MXn =
pKa E12 for Mn(VVI) (V vs ferrocene)
K(OTf) 1625 0616Na(OTf) 1477 0591Ba(OTf)2 1336 0805Sr(OTf)2 1318 0880
Na+(expected)
[Na+(experimental) - Na+(expected)]
0723
0591-0723 =-0132
Data plotted from reference [31] of the main text
20
Table S3 Masses of species obtained with their calculated values
[CuL]+ 10 eqv MXn
salts
Figure Species detected
with charge
Experimental
Mass (mz)
Calculated
Mass
(mz)
[CuL]M
[(CuL)2Li]+ 72116 72114 21Li(ClO4)3H2O S3
[(CuL)Li]+ 36407 36408 11
[(CuL)2Zn(ClO4)]+ 87701 87701 21
[(CuL)2Zn]2+ 39003 39003 21
Zn(ClO4)26H2O S4
[(CuL)Zn(ClO4)]+ 51994 51994 11
[(CuL)2Cd(ClO4)]+ 92698 92698 21
[(CuL)2Cd]2+ 41402 41401 21
Cd(ClO4)26H2O S5
[(CuL)Cd(ClO4)]+ 56991 56991 11
[(CuL)2Pr(NO3)2]+ 97903 97902 21Pr(NO3)36H2O S6
[(CuL)Pr(NO3)2]+ 62196 62196 11
[(CuL)2Nd(NO3)2]+ 98001 98001 21Nd(NO3)36H2O S7
[(CuL)Nd(NO3)2]+ 62295 62294 11
[(CuL)2Sm(NO3)2]+ 99002 99002 21Sm(NO3)36H2O S8
[(CuL)Sm(NO3)2]+ 63296 63296 11
Table S4 Comparison of HOMO-LUMO gap with the overall electrochemical shift in 11 adducts
Complex Relative stabilization of HOMO-LUMO gap (max) with
respect to [CuL]+K+
(meV)
Expected shift with respect to [CuL]+K+
1198981198901198811 119890
= 119898119881
[E12 (ox) - E12 (red)] =E12 observed from
DPV (V)
Relative shift of E12 with respect to
[CuL]+K+
(mV)
[CuL]+K+ (943-943) = 0 0466-(-1487) =1953 1953-1953 = 0
[CuL]+Na+ (4868-943) = 3925 0487-(-1412) =1899 1953-1899 = 54
[CuL]+Li+ (19920-943) = 18977 0555-(-1207) = 1762 1953-1762 = 191
[CuL]+Ca2+ (25807-943) = 24864 0589-(-1111) = 1700 1953-1700 = 253
[CuL]+Mg2+ (28543-943) = 27600 0623-(-1107) = 1730 1953-1730 = 223
21
Table S5 Summary of UV-Vis and electrochemical properties of complexes 1 and 2
Complex 1 [CuL]+10 equiv
K+
Complex 2 [CuL]+10 equiv
Zn2+
max ( LMCT) nm 3655 362 344 nm 3325
E12 (ox) (V) from
DPV
0493 0898 0466 0913 0471 0612
0920
0652 0784
E12 (red) (V) from
DPV
-1175 (hump) -
1459
-1487 -0875 (hump)
-1011 -1477
Not done
2
Fig S2 BenesiminusHilderbrand plot for [CuL] + Li+ (upper panel) [CuL] + Zn2+ (lower panel left
side) and [CuL] + Cd2+ (lower panel right side) complex formation
3
Fig S3 Representative ESI mass spectrum of [CuL]ndashLi+ mixture in acetonitrile
Fig S4 Representative ESI mass spectrum of [CuL]ndashZn2+ mixture in acetonitrile
4
Fig S5 Representative ESI mass spectrum of [CuL]ndashCd2+ mixture in acetonitrile
Fig S6 Representative ESI mass spectrum of [CuL]ndashPr3+ mixture in acetonitrile
5
Fig S7 Representative ESI mass spectrum of [CuL]ndashNd3+ mixture in acetonitrile
Fig S8 Representative ESI mass spectrum of [CuL]ndashSm3+ mixture in acetonitrile
6
Fig S9 Dependence of LMCT energy bands on pKa of M(aqua)n+ ion as a measure of its Lewis acidity in presence of 100 equivalent of MprimeXn salts
Fig S10 Potential scan of unbound [CuL] and [CuL]+K+ upto first oxidation step
7
Fig S11 Left Multicycle CV of [CuL] Right CV of [CuL] at different concentration at 300 mVS scan rate in acetonitrile
Fig S12 Differential pulse voltametric (DPV) analysis of unbound [CuL] and [CuL]+K+
8
Fig S13 Cyclic voltammograms of electrochemical reduction of unbound [CuL] (upper panel
left side) and [CuL] + 10 equiv of KPF6 (upper panel right side) in acetonitrile at multiple scan
rate (mVS-1) and Differential pulse voltametric (DPV) analysis of unbound [CuL] and
[CuL]+K+(lower panel) at a scan rate of 20 mVS-1
9
Fig S14 Left Panel Cyclic voltammograms of Cu(III) couple in presence of 10 equiv of
specified redox-inactive metal ions in acetonitrile at a scan rate of 300 mVs-1 Right panel DPV
analysis of the corresponding mixtures at a scan rate of 20 mVs-1
10
Fig S15 Top UV-VIS spectra Middle CV (300 mVs-1 scan rate) and Bottom DPV (20 mVs-1 scan rate) of complex 1 at different potential range in presence of 100 equiv of TBAHFP in acetonitrile
11
Fig S16 Top UV-VIS spectra Middle CV (300 mVs-1 scan rate) and Bottom DPV (20 mVs-1 scan rate) of complex 2 at different potential range in presence of 100 equiv of TBAHFP in acetonitrile
12
Fig S17 Dependence of half-wave potentials (E12) of electrochemical reduction of the
heterometallic complexes ([(CuL)M]n+) vs pKa of M(aqua)n+ ions as measure of their Lewis
acidity
Fig S18 Electrochemical response of [CuL] in acetonitrile upon incremental addition of aquous
acetonirile (left) and the corresponding change in molar extinction coefficient of LMCT band
(right)
13
Fig S19 Electrochemical response of [CuL] + 10 eqv Zn2+ in acetonitrile upon incremental
addition of aquous acetonirile (left) and the corresponding change in molar extinction coefficient
of LMCT band (right)
Fig S20 Electrochemical response of [CuL] + 10 eqv Mg2+ in acetonitrile upon incremental
addition of aquous acetonirile (left) and the corresponding change in molar extinction coefficient
of LMCT band (right)
14
Fig S21 Correlation of shift of oxidation peak potential with equivalent of water added for
[CuL]+Mn+( Mn+ = Pr3+ Zn2+ Mg2+) (Solid line is guide for eye)
Fig S22 Correlation of change of molar absorptivity with equivalent of water added for
[CuL]+Mn+( Mn+ = Pr3+ Zn2+ Mg2+) (Solid line is guide for eye)
15
Fig S23 Correlation of the shift of oxidation peak potential with the change of molar extinction
coefficient of [CuL] in acetonitrile upon incremental addition of aquous acetonirile
Fig S24 Correlation of the shift of oxidation peak potential with the change of molar extinction
coefficient of [CuL]+10 eqv Zn2+ in acetonitrile upon incremental addition of aquous
acetonirile
16
Fig S25 Correlation of the shift of oxidation peak potential with the change of molar extinction
coefficient of [CuL]+10 eqv Mg2+ in acetonitrile upon incremental addition of aquous
acetonirile
Table S1 List of bond lengths (Aring) and bond angles (ordm) of complexes 1 and 2
M = K M = Zn
M(1)O(1) 2020(6) 2000(4)
M(1)O(2) 2179(5) 2279(5)
M(1)O(3) 2012(5) 1986(4)
M(1)O(4) 2184(6)) 2345(5)
M(1)O(5) 2058(6) 2062(5)
M(1)O(6) 2037(5) 2031(5)
Cu(1)O(1) 1920(5) 1909(5)
Cu(1)O(2) 1944(4) 1917(4)
Cu(1)N(1) 2004(6) 1982(6)
Cu(1)N(2) 1937(7) 1913(6)
Cu(2)O(3) 1909(5) 1922(5)
17
Cu(2)O(4) 1937(5) 1896(4)
Cu(2)N(3) 1966(5) 1963(5)
Cu(2)N(4) 1933(7) 1927(5)
O(1)M(1)O(2) 7448(18) 7182(17)
O(1)M(1)O(3) 1567(2) 14831(19)
O(1)M(1)O(4) 891(2) 8456(17)
O(1)M(1)O(5) 1020(2) 1061(2)
O(1)M(1)O(6) 942(2) 954(2)
O(2)M(1)O(3) 8738(19) 8400(18)
O(2)M(1)O(4) 813(2) 7719(17)
O(2)M(1)O(5) 929(2) 9441(18)
O(2)M(1)O(6) 1684(2) 16616(18)
O(3)M(1)O(4) 734(2) 7002(16)
O(3)M(1)O(5) 933(2) 9563(19)
O(3)M(1)O(6) 1028(2) 1058(2)
O(4)M(1)O(5) 1657(2) 16385(18)
O(4)M(1)O(6) 963(2) 9675(18)
O(5)M(1)O(6) 919(2) 943(2)
O(1)Cu(1)O(2) 824(2) 8238(18)
O(1)Cu(1)N(1) 905(2) 902(2)
O(1)Cu(1)N(2) 1693(3) 1690(2)
O(2)Cu(1)N(1) 1633(2) 1656(2)
O(2)Cu(1)N(2) 918(3) 920(2)
N(1)Cu(1)N(2) 974(3) 973(2)
O(2)Cu(2)O(3) 7047(16) 6993(16)
O(2)Cu(2)O(4) 684(2) 7092(17)
O(2)Cu(2)N(3) 982(2) 9683(17)
O(2)Cu(2)N(4) 1134(2) 11492(18)
18
O(3)Cu(2)O(4) 815(2) 8190(18)
O(3)Cu(2)N(3) 903(2) 901(2)
O(3)Cu(2)N(4) 1712(2) 1717(2)
O(4)Cu(2)N(3) 1660(3) 1671(2)
O(4)Cu(2)N(4) 925(3) 932(2)
N(3)Cu(2)N(4) 968(3) 959(2)
Table S2 Correlation of electrochemical response of previously reported 11 metallohost redox-inactive ion adducts derived from bicompartmental macrocyclic ligands containing adjacent N2O2 and 18-crown-6 like cavity with pKa of corresponding metal-aqua complex
[MnL](PF6)+MXn in acetonitrile MXn =
pKa E12 for Mn(IIIII) (V vs SCE)
KPF6 1625 0025LiClO4 1382 0055Ba(OTf)2 1336 0200Ca(OTf)2 1260 0245
Li+(expected)
[Li+(experimental) - Li+(expected)]
0176
0055 - 0176 =-0121
Data plotted from reference [16] of the main text
[NiL]+MXn in acetonitrileMXn =
pKa EPC for Ni(III)(V vs ferrocene)
NaPF6 1477 -165Ca(OTf)2 1260 -142Nd(OTf)3 843a -118Y(OTf)3 804a -122
Y3+(expected)
[Y3+(experimental) - Y3+(expected)]
-113
-122-(-113) =-009
aobtained from ref Data plotted from reference [17] of the main text
19
[56] of main text[CoL] + MXn in DMF MXn =
pKa E12 for Co(III)(V vs ferrocene)
K(OTf) 1625 -158Na(OTf) 1477 -158Ba(OTf)2 1336 -148Sr(OTf)2 1318 -144Ca(OTf)2 1260 -141
Na+(expected)
[Na+(experimental) - Na+(expected)]
-1515
-158 - (-1515)=-0065
Data plotted from reference [18] of the main text
[CuL]+Mn+ in DMSO Mn+=
pKa E12 for Cu(III)(V vs AgAgCl)
K+ 1625 -1277Na+ 1477 -1279Li+ 1382 -1286Ba2+ 1336 -1119Na+(expected)
[Na+(experimental) - Na+(expected)]
Li+(expected)
[Li+(experimental) - Li+(expected)]
-1185-1279-(-1185)=-0094
-1134-1286-(-1134)=-0152
Data plotted from reference [19] of the main text Line is guide for eye
[Mn(N)L] + MXn in acetonitrile MXn =
pKa E12 for Mn(VVI) (V vs ferrocene)
K(OTf) 1625 0616Na(OTf) 1477 0591Ba(OTf)2 1336 0805Sr(OTf)2 1318 0880
Na+(expected)
[Na+(experimental) - Na+(expected)]
0723
0591-0723 =-0132
Data plotted from reference [31] of the main text
20
Table S3 Masses of species obtained with their calculated values
[CuL]+ 10 eqv MXn
salts
Figure Species detected
with charge
Experimental
Mass (mz)
Calculated
Mass
(mz)
[CuL]M
[(CuL)2Li]+ 72116 72114 21Li(ClO4)3H2O S3
[(CuL)Li]+ 36407 36408 11
[(CuL)2Zn(ClO4)]+ 87701 87701 21
[(CuL)2Zn]2+ 39003 39003 21
Zn(ClO4)26H2O S4
[(CuL)Zn(ClO4)]+ 51994 51994 11
[(CuL)2Cd(ClO4)]+ 92698 92698 21
[(CuL)2Cd]2+ 41402 41401 21
Cd(ClO4)26H2O S5
[(CuL)Cd(ClO4)]+ 56991 56991 11
[(CuL)2Pr(NO3)2]+ 97903 97902 21Pr(NO3)36H2O S6
[(CuL)Pr(NO3)2]+ 62196 62196 11
[(CuL)2Nd(NO3)2]+ 98001 98001 21Nd(NO3)36H2O S7
[(CuL)Nd(NO3)2]+ 62295 62294 11
[(CuL)2Sm(NO3)2]+ 99002 99002 21Sm(NO3)36H2O S8
[(CuL)Sm(NO3)2]+ 63296 63296 11
Table S4 Comparison of HOMO-LUMO gap with the overall electrochemical shift in 11 adducts
Complex Relative stabilization of HOMO-LUMO gap (max) with
respect to [CuL]+K+
(meV)
Expected shift with respect to [CuL]+K+
1198981198901198811 119890
= 119898119881
[E12 (ox) - E12 (red)] =E12 observed from
DPV (V)
Relative shift of E12 with respect to
[CuL]+K+
(mV)
[CuL]+K+ (943-943) = 0 0466-(-1487) =1953 1953-1953 = 0
[CuL]+Na+ (4868-943) = 3925 0487-(-1412) =1899 1953-1899 = 54
[CuL]+Li+ (19920-943) = 18977 0555-(-1207) = 1762 1953-1762 = 191
[CuL]+Ca2+ (25807-943) = 24864 0589-(-1111) = 1700 1953-1700 = 253
[CuL]+Mg2+ (28543-943) = 27600 0623-(-1107) = 1730 1953-1730 = 223
21
Table S5 Summary of UV-Vis and electrochemical properties of complexes 1 and 2
Complex 1 [CuL]+10 equiv
K+
Complex 2 [CuL]+10 equiv
Zn2+
max ( LMCT) nm 3655 362 344 nm 3325
E12 (ox) (V) from
DPV
0493 0898 0466 0913 0471 0612
0920
0652 0784
E12 (red) (V) from
DPV
-1175 (hump) -
1459
-1487 -0875 (hump)
-1011 -1477
Not done
3
Fig S3 Representative ESI mass spectrum of [CuL]ndashLi+ mixture in acetonitrile
Fig S4 Representative ESI mass spectrum of [CuL]ndashZn2+ mixture in acetonitrile
4
Fig S5 Representative ESI mass spectrum of [CuL]ndashCd2+ mixture in acetonitrile
Fig S6 Representative ESI mass spectrum of [CuL]ndashPr3+ mixture in acetonitrile
5
Fig S7 Representative ESI mass spectrum of [CuL]ndashNd3+ mixture in acetonitrile
Fig S8 Representative ESI mass spectrum of [CuL]ndashSm3+ mixture in acetonitrile
6
Fig S9 Dependence of LMCT energy bands on pKa of M(aqua)n+ ion as a measure of its Lewis acidity in presence of 100 equivalent of MprimeXn salts
Fig S10 Potential scan of unbound [CuL] and [CuL]+K+ upto first oxidation step
7
Fig S11 Left Multicycle CV of [CuL] Right CV of [CuL] at different concentration at 300 mVS scan rate in acetonitrile
Fig S12 Differential pulse voltametric (DPV) analysis of unbound [CuL] and [CuL]+K+
8
Fig S13 Cyclic voltammograms of electrochemical reduction of unbound [CuL] (upper panel
left side) and [CuL] + 10 equiv of KPF6 (upper panel right side) in acetonitrile at multiple scan
rate (mVS-1) and Differential pulse voltametric (DPV) analysis of unbound [CuL] and
[CuL]+K+(lower panel) at a scan rate of 20 mVS-1
9
Fig S14 Left Panel Cyclic voltammograms of Cu(III) couple in presence of 10 equiv of
specified redox-inactive metal ions in acetonitrile at a scan rate of 300 mVs-1 Right panel DPV
analysis of the corresponding mixtures at a scan rate of 20 mVs-1
10
Fig S15 Top UV-VIS spectra Middle CV (300 mVs-1 scan rate) and Bottom DPV (20 mVs-1 scan rate) of complex 1 at different potential range in presence of 100 equiv of TBAHFP in acetonitrile
11
Fig S16 Top UV-VIS spectra Middle CV (300 mVs-1 scan rate) and Bottom DPV (20 mVs-1 scan rate) of complex 2 at different potential range in presence of 100 equiv of TBAHFP in acetonitrile
12
Fig S17 Dependence of half-wave potentials (E12) of electrochemical reduction of the
heterometallic complexes ([(CuL)M]n+) vs pKa of M(aqua)n+ ions as measure of their Lewis
acidity
Fig S18 Electrochemical response of [CuL] in acetonitrile upon incremental addition of aquous
acetonirile (left) and the corresponding change in molar extinction coefficient of LMCT band
(right)
13
Fig S19 Electrochemical response of [CuL] + 10 eqv Zn2+ in acetonitrile upon incremental
addition of aquous acetonirile (left) and the corresponding change in molar extinction coefficient
of LMCT band (right)
Fig S20 Electrochemical response of [CuL] + 10 eqv Mg2+ in acetonitrile upon incremental
addition of aquous acetonirile (left) and the corresponding change in molar extinction coefficient
of LMCT band (right)
14
Fig S21 Correlation of shift of oxidation peak potential with equivalent of water added for
[CuL]+Mn+( Mn+ = Pr3+ Zn2+ Mg2+) (Solid line is guide for eye)
Fig S22 Correlation of change of molar absorptivity with equivalent of water added for
[CuL]+Mn+( Mn+ = Pr3+ Zn2+ Mg2+) (Solid line is guide for eye)
15
Fig S23 Correlation of the shift of oxidation peak potential with the change of molar extinction
coefficient of [CuL] in acetonitrile upon incremental addition of aquous acetonirile
Fig S24 Correlation of the shift of oxidation peak potential with the change of molar extinction
coefficient of [CuL]+10 eqv Zn2+ in acetonitrile upon incremental addition of aquous
acetonirile
16
Fig S25 Correlation of the shift of oxidation peak potential with the change of molar extinction
coefficient of [CuL]+10 eqv Mg2+ in acetonitrile upon incremental addition of aquous
acetonirile
Table S1 List of bond lengths (Aring) and bond angles (ordm) of complexes 1 and 2
M = K M = Zn
M(1)O(1) 2020(6) 2000(4)
M(1)O(2) 2179(5) 2279(5)
M(1)O(3) 2012(5) 1986(4)
M(1)O(4) 2184(6)) 2345(5)
M(1)O(5) 2058(6) 2062(5)
M(1)O(6) 2037(5) 2031(5)
Cu(1)O(1) 1920(5) 1909(5)
Cu(1)O(2) 1944(4) 1917(4)
Cu(1)N(1) 2004(6) 1982(6)
Cu(1)N(2) 1937(7) 1913(6)
Cu(2)O(3) 1909(5) 1922(5)
17
Cu(2)O(4) 1937(5) 1896(4)
Cu(2)N(3) 1966(5) 1963(5)
Cu(2)N(4) 1933(7) 1927(5)
O(1)M(1)O(2) 7448(18) 7182(17)
O(1)M(1)O(3) 1567(2) 14831(19)
O(1)M(1)O(4) 891(2) 8456(17)
O(1)M(1)O(5) 1020(2) 1061(2)
O(1)M(1)O(6) 942(2) 954(2)
O(2)M(1)O(3) 8738(19) 8400(18)
O(2)M(1)O(4) 813(2) 7719(17)
O(2)M(1)O(5) 929(2) 9441(18)
O(2)M(1)O(6) 1684(2) 16616(18)
O(3)M(1)O(4) 734(2) 7002(16)
O(3)M(1)O(5) 933(2) 9563(19)
O(3)M(1)O(6) 1028(2) 1058(2)
O(4)M(1)O(5) 1657(2) 16385(18)
O(4)M(1)O(6) 963(2) 9675(18)
O(5)M(1)O(6) 919(2) 943(2)
O(1)Cu(1)O(2) 824(2) 8238(18)
O(1)Cu(1)N(1) 905(2) 902(2)
O(1)Cu(1)N(2) 1693(3) 1690(2)
O(2)Cu(1)N(1) 1633(2) 1656(2)
O(2)Cu(1)N(2) 918(3) 920(2)
N(1)Cu(1)N(2) 974(3) 973(2)
O(2)Cu(2)O(3) 7047(16) 6993(16)
O(2)Cu(2)O(4) 684(2) 7092(17)
O(2)Cu(2)N(3) 982(2) 9683(17)
O(2)Cu(2)N(4) 1134(2) 11492(18)
18
O(3)Cu(2)O(4) 815(2) 8190(18)
O(3)Cu(2)N(3) 903(2) 901(2)
O(3)Cu(2)N(4) 1712(2) 1717(2)
O(4)Cu(2)N(3) 1660(3) 1671(2)
O(4)Cu(2)N(4) 925(3) 932(2)
N(3)Cu(2)N(4) 968(3) 959(2)
Table S2 Correlation of electrochemical response of previously reported 11 metallohost redox-inactive ion adducts derived from bicompartmental macrocyclic ligands containing adjacent N2O2 and 18-crown-6 like cavity with pKa of corresponding metal-aqua complex
[MnL](PF6)+MXn in acetonitrile MXn =
pKa E12 for Mn(IIIII) (V vs SCE)
KPF6 1625 0025LiClO4 1382 0055Ba(OTf)2 1336 0200Ca(OTf)2 1260 0245
Li+(expected)
[Li+(experimental) - Li+(expected)]
0176
0055 - 0176 =-0121
Data plotted from reference [16] of the main text
[NiL]+MXn in acetonitrileMXn =
pKa EPC for Ni(III)(V vs ferrocene)
NaPF6 1477 -165Ca(OTf)2 1260 -142Nd(OTf)3 843a -118Y(OTf)3 804a -122
Y3+(expected)
[Y3+(experimental) - Y3+(expected)]
-113
-122-(-113) =-009
aobtained from ref Data plotted from reference [17] of the main text
19
[56] of main text[CoL] + MXn in DMF MXn =
pKa E12 for Co(III)(V vs ferrocene)
K(OTf) 1625 -158Na(OTf) 1477 -158Ba(OTf)2 1336 -148Sr(OTf)2 1318 -144Ca(OTf)2 1260 -141
Na+(expected)
[Na+(experimental) - Na+(expected)]
-1515
-158 - (-1515)=-0065
Data plotted from reference [18] of the main text
[CuL]+Mn+ in DMSO Mn+=
pKa E12 for Cu(III)(V vs AgAgCl)
K+ 1625 -1277Na+ 1477 -1279Li+ 1382 -1286Ba2+ 1336 -1119Na+(expected)
[Na+(experimental) - Na+(expected)]
Li+(expected)
[Li+(experimental) - Li+(expected)]
-1185-1279-(-1185)=-0094
-1134-1286-(-1134)=-0152
Data plotted from reference [19] of the main text Line is guide for eye
[Mn(N)L] + MXn in acetonitrile MXn =
pKa E12 for Mn(VVI) (V vs ferrocene)
K(OTf) 1625 0616Na(OTf) 1477 0591Ba(OTf)2 1336 0805Sr(OTf)2 1318 0880
Na+(expected)
[Na+(experimental) - Na+(expected)]
0723
0591-0723 =-0132
Data plotted from reference [31] of the main text
20
Table S3 Masses of species obtained with their calculated values
[CuL]+ 10 eqv MXn
salts
Figure Species detected
with charge
Experimental
Mass (mz)
Calculated
Mass
(mz)
[CuL]M
[(CuL)2Li]+ 72116 72114 21Li(ClO4)3H2O S3
[(CuL)Li]+ 36407 36408 11
[(CuL)2Zn(ClO4)]+ 87701 87701 21
[(CuL)2Zn]2+ 39003 39003 21
Zn(ClO4)26H2O S4
[(CuL)Zn(ClO4)]+ 51994 51994 11
[(CuL)2Cd(ClO4)]+ 92698 92698 21
[(CuL)2Cd]2+ 41402 41401 21
Cd(ClO4)26H2O S5
[(CuL)Cd(ClO4)]+ 56991 56991 11
[(CuL)2Pr(NO3)2]+ 97903 97902 21Pr(NO3)36H2O S6
[(CuL)Pr(NO3)2]+ 62196 62196 11
[(CuL)2Nd(NO3)2]+ 98001 98001 21Nd(NO3)36H2O S7
[(CuL)Nd(NO3)2]+ 62295 62294 11
[(CuL)2Sm(NO3)2]+ 99002 99002 21Sm(NO3)36H2O S8
[(CuL)Sm(NO3)2]+ 63296 63296 11
Table S4 Comparison of HOMO-LUMO gap with the overall electrochemical shift in 11 adducts
Complex Relative stabilization of HOMO-LUMO gap (max) with
respect to [CuL]+K+
(meV)
Expected shift with respect to [CuL]+K+
1198981198901198811 119890
= 119898119881
[E12 (ox) - E12 (red)] =E12 observed from
DPV (V)
Relative shift of E12 with respect to
[CuL]+K+
(mV)
[CuL]+K+ (943-943) = 0 0466-(-1487) =1953 1953-1953 = 0
[CuL]+Na+ (4868-943) = 3925 0487-(-1412) =1899 1953-1899 = 54
[CuL]+Li+ (19920-943) = 18977 0555-(-1207) = 1762 1953-1762 = 191
[CuL]+Ca2+ (25807-943) = 24864 0589-(-1111) = 1700 1953-1700 = 253
[CuL]+Mg2+ (28543-943) = 27600 0623-(-1107) = 1730 1953-1730 = 223
21
Table S5 Summary of UV-Vis and electrochemical properties of complexes 1 and 2
Complex 1 [CuL]+10 equiv
K+
Complex 2 [CuL]+10 equiv
Zn2+
max ( LMCT) nm 3655 362 344 nm 3325
E12 (ox) (V) from
DPV
0493 0898 0466 0913 0471 0612
0920
0652 0784
E12 (red) (V) from
DPV
-1175 (hump) -
1459
-1487 -0875 (hump)
-1011 -1477
Not done
4
Fig S5 Representative ESI mass spectrum of [CuL]ndashCd2+ mixture in acetonitrile
Fig S6 Representative ESI mass spectrum of [CuL]ndashPr3+ mixture in acetonitrile
5
Fig S7 Representative ESI mass spectrum of [CuL]ndashNd3+ mixture in acetonitrile
Fig S8 Representative ESI mass spectrum of [CuL]ndashSm3+ mixture in acetonitrile
6
Fig S9 Dependence of LMCT energy bands on pKa of M(aqua)n+ ion as a measure of its Lewis acidity in presence of 100 equivalent of MprimeXn salts
Fig S10 Potential scan of unbound [CuL] and [CuL]+K+ upto first oxidation step
7
Fig S11 Left Multicycle CV of [CuL] Right CV of [CuL] at different concentration at 300 mVS scan rate in acetonitrile
Fig S12 Differential pulse voltametric (DPV) analysis of unbound [CuL] and [CuL]+K+
8
Fig S13 Cyclic voltammograms of electrochemical reduction of unbound [CuL] (upper panel
left side) and [CuL] + 10 equiv of KPF6 (upper panel right side) in acetonitrile at multiple scan
rate (mVS-1) and Differential pulse voltametric (DPV) analysis of unbound [CuL] and
[CuL]+K+(lower panel) at a scan rate of 20 mVS-1
9
Fig S14 Left Panel Cyclic voltammograms of Cu(III) couple in presence of 10 equiv of
specified redox-inactive metal ions in acetonitrile at a scan rate of 300 mVs-1 Right panel DPV
analysis of the corresponding mixtures at a scan rate of 20 mVs-1
10
Fig S15 Top UV-VIS spectra Middle CV (300 mVs-1 scan rate) and Bottom DPV (20 mVs-1 scan rate) of complex 1 at different potential range in presence of 100 equiv of TBAHFP in acetonitrile
11
Fig S16 Top UV-VIS spectra Middle CV (300 mVs-1 scan rate) and Bottom DPV (20 mVs-1 scan rate) of complex 2 at different potential range in presence of 100 equiv of TBAHFP in acetonitrile
12
Fig S17 Dependence of half-wave potentials (E12) of electrochemical reduction of the
heterometallic complexes ([(CuL)M]n+) vs pKa of M(aqua)n+ ions as measure of their Lewis
acidity
Fig S18 Electrochemical response of [CuL] in acetonitrile upon incremental addition of aquous
acetonirile (left) and the corresponding change in molar extinction coefficient of LMCT band
(right)
13
Fig S19 Electrochemical response of [CuL] + 10 eqv Zn2+ in acetonitrile upon incremental
addition of aquous acetonirile (left) and the corresponding change in molar extinction coefficient
of LMCT band (right)
Fig S20 Electrochemical response of [CuL] + 10 eqv Mg2+ in acetonitrile upon incremental
addition of aquous acetonirile (left) and the corresponding change in molar extinction coefficient
of LMCT band (right)
14
Fig S21 Correlation of shift of oxidation peak potential with equivalent of water added for
[CuL]+Mn+( Mn+ = Pr3+ Zn2+ Mg2+) (Solid line is guide for eye)
Fig S22 Correlation of change of molar absorptivity with equivalent of water added for
[CuL]+Mn+( Mn+ = Pr3+ Zn2+ Mg2+) (Solid line is guide for eye)
15
Fig S23 Correlation of the shift of oxidation peak potential with the change of molar extinction
coefficient of [CuL] in acetonitrile upon incremental addition of aquous acetonirile
Fig S24 Correlation of the shift of oxidation peak potential with the change of molar extinction
coefficient of [CuL]+10 eqv Zn2+ in acetonitrile upon incremental addition of aquous
acetonirile
16
Fig S25 Correlation of the shift of oxidation peak potential with the change of molar extinction
coefficient of [CuL]+10 eqv Mg2+ in acetonitrile upon incremental addition of aquous
acetonirile
Table S1 List of bond lengths (Aring) and bond angles (ordm) of complexes 1 and 2
M = K M = Zn
M(1)O(1) 2020(6) 2000(4)
M(1)O(2) 2179(5) 2279(5)
M(1)O(3) 2012(5) 1986(4)
M(1)O(4) 2184(6)) 2345(5)
M(1)O(5) 2058(6) 2062(5)
M(1)O(6) 2037(5) 2031(5)
Cu(1)O(1) 1920(5) 1909(5)
Cu(1)O(2) 1944(4) 1917(4)
Cu(1)N(1) 2004(6) 1982(6)
Cu(1)N(2) 1937(7) 1913(6)
Cu(2)O(3) 1909(5) 1922(5)
17
Cu(2)O(4) 1937(5) 1896(4)
Cu(2)N(3) 1966(5) 1963(5)
Cu(2)N(4) 1933(7) 1927(5)
O(1)M(1)O(2) 7448(18) 7182(17)
O(1)M(1)O(3) 1567(2) 14831(19)
O(1)M(1)O(4) 891(2) 8456(17)
O(1)M(1)O(5) 1020(2) 1061(2)
O(1)M(1)O(6) 942(2) 954(2)
O(2)M(1)O(3) 8738(19) 8400(18)
O(2)M(1)O(4) 813(2) 7719(17)
O(2)M(1)O(5) 929(2) 9441(18)
O(2)M(1)O(6) 1684(2) 16616(18)
O(3)M(1)O(4) 734(2) 7002(16)
O(3)M(1)O(5) 933(2) 9563(19)
O(3)M(1)O(6) 1028(2) 1058(2)
O(4)M(1)O(5) 1657(2) 16385(18)
O(4)M(1)O(6) 963(2) 9675(18)
O(5)M(1)O(6) 919(2) 943(2)
O(1)Cu(1)O(2) 824(2) 8238(18)
O(1)Cu(1)N(1) 905(2) 902(2)
O(1)Cu(1)N(2) 1693(3) 1690(2)
O(2)Cu(1)N(1) 1633(2) 1656(2)
O(2)Cu(1)N(2) 918(3) 920(2)
N(1)Cu(1)N(2) 974(3) 973(2)
O(2)Cu(2)O(3) 7047(16) 6993(16)
O(2)Cu(2)O(4) 684(2) 7092(17)
O(2)Cu(2)N(3) 982(2) 9683(17)
O(2)Cu(2)N(4) 1134(2) 11492(18)
18
O(3)Cu(2)O(4) 815(2) 8190(18)
O(3)Cu(2)N(3) 903(2) 901(2)
O(3)Cu(2)N(4) 1712(2) 1717(2)
O(4)Cu(2)N(3) 1660(3) 1671(2)
O(4)Cu(2)N(4) 925(3) 932(2)
N(3)Cu(2)N(4) 968(3) 959(2)
Table S2 Correlation of electrochemical response of previously reported 11 metallohost redox-inactive ion adducts derived from bicompartmental macrocyclic ligands containing adjacent N2O2 and 18-crown-6 like cavity with pKa of corresponding metal-aqua complex
[MnL](PF6)+MXn in acetonitrile MXn =
pKa E12 for Mn(IIIII) (V vs SCE)
KPF6 1625 0025LiClO4 1382 0055Ba(OTf)2 1336 0200Ca(OTf)2 1260 0245
Li+(expected)
[Li+(experimental) - Li+(expected)]
0176
0055 - 0176 =-0121
Data plotted from reference [16] of the main text
[NiL]+MXn in acetonitrileMXn =
pKa EPC for Ni(III)(V vs ferrocene)
NaPF6 1477 -165Ca(OTf)2 1260 -142Nd(OTf)3 843a -118Y(OTf)3 804a -122
Y3+(expected)
[Y3+(experimental) - Y3+(expected)]
-113
-122-(-113) =-009
aobtained from ref Data plotted from reference [17] of the main text
19
[56] of main text[CoL] + MXn in DMF MXn =
pKa E12 for Co(III)(V vs ferrocene)
K(OTf) 1625 -158Na(OTf) 1477 -158Ba(OTf)2 1336 -148Sr(OTf)2 1318 -144Ca(OTf)2 1260 -141
Na+(expected)
[Na+(experimental) - Na+(expected)]
-1515
-158 - (-1515)=-0065
Data plotted from reference [18] of the main text
[CuL]+Mn+ in DMSO Mn+=
pKa E12 for Cu(III)(V vs AgAgCl)
K+ 1625 -1277Na+ 1477 -1279Li+ 1382 -1286Ba2+ 1336 -1119Na+(expected)
[Na+(experimental) - Na+(expected)]
Li+(expected)
[Li+(experimental) - Li+(expected)]
-1185-1279-(-1185)=-0094
-1134-1286-(-1134)=-0152
Data plotted from reference [19] of the main text Line is guide for eye
[Mn(N)L] + MXn in acetonitrile MXn =
pKa E12 for Mn(VVI) (V vs ferrocene)
K(OTf) 1625 0616Na(OTf) 1477 0591Ba(OTf)2 1336 0805Sr(OTf)2 1318 0880
Na+(expected)
[Na+(experimental) - Na+(expected)]
0723
0591-0723 =-0132
Data plotted from reference [31] of the main text
20
Table S3 Masses of species obtained with their calculated values
[CuL]+ 10 eqv MXn
salts
Figure Species detected
with charge
Experimental
Mass (mz)
Calculated
Mass
(mz)
[CuL]M
[(CuL)2Li]+ 72116 72114 21Li(ClO4)3H2O S3
[(CuL)Li]+ 36407 36408 11
[(CuL)2Zn(ClO4)]+ 87701 87701 21
[(CuL)2Zn]2+ 39003 39003 21
Zn(ClO4)26H2O S4
[(CuL)Zn(ClO4)]+ 51994 51994 11
[(CuL)2Cd(ClO4)]+ 92698 92698 21
[(CuL)2Cd]2+ 41402 41401 21
Cd(ClO4)26H2O S5
[(CuL)Cd(ClO4)]+ 56991 56991 11
[(CuL)2Pr(NO3)2]+ 97903 97902 21Pr(NO3)36H2O S6
[(CuL)Pr(NO3)2]+ 62196 62196 11
[(CuL)2Nd(NO3)2]+ 98001 98001 21Nd(NO3)36H2O S7
[(CuL)Nd(NO3)2]+ 62295 62294 11
[(CuL)2Sm(NO3)2]+ 99002 99002 21Sm(NO3)36H2O S8
[(CuL)Sm(NO3)2]+ 63296 63296 11
Table S4 Comparison of HOMO-LUMO gap with the overall electrochemical shift in 11 adducts
Complex Relative stabilization of HOMO-LUMO gap (max) with
respect to [CuL]+K+
(meV)
Expected shift with respect to [CuL]+K+
1198981198901198811 119890
= 119898119881
[E12 (ox) - E12 (red)] =E12 observed from
DPV (V)
Relative shift of E12 with respect to
[CuL]+K+
(mV)
[CuL]+K+ (943-943) = 0 0466-(-1487) =1953 1953-1953 = 0
[CuL]+Na+ (4868-943) = 3925 0487-(-1412) =1899 1953-1899 = 54
[CuL]+Li+ (19920-943) = 18977 0555-(-1207) = 1762 1953-1762 = 191
[CuL]+Ca2+ (25807-943) = 24864 0589-(-1111) = 1700 1953-1700 = 253
[CuL]+Mg2+ (28543-943) = 27600 0623-(-1107) = 1730 1953-1730 = 223
21
Table S5 Summary of UV-Vis and electrochemical properties of complexes 1 and 2
Complex 1 [CuL]+10 equiv
K+
Complex 2 [CuL]+10 equiv
Zn2+
max ( LMCT) nm 3655 362 344 nm 3325
E12 (ox) (V) from
DPV
0493 0898 0466 0913 0471 0612
0920
0652 0784
E12 (red) (V) from
DPV
-1175 (hump) -
1459
-1487 -0875 (hump)
-1011 -1477
Not done
5
Fig S7 Representative ESI mass spectrum of [CuL]ndashNd3+ mixture in acetonitrile
Fig S8 Representative ESI mass spectrum of [CuL]ndashSm3+ mixture in acetonitrile
6
Fig S9 Dependence of LMCT energy bands on pKa of M(aqua)n+ ion as a measure of its Lewis acidity in presence of 100 equivalent of MprimeXn salts
Fig S10 Potential scan of unbound [CuL] and [CuL]+K+ upto first oxidation step
7
Fig S11 Left Multicycle CV of [CuL] Right CV of [CuL] at different concentration at 300 mVS scan rate in acetonitrile
Fig S12 Differential pulse voltametric (DPV) analysis of unbound [CuL] and [CuL]+K+
8
Fig S13 Cyclic voltammograms of electrochemical reduction of unbound [CuL] (upper panel
left side) and [CuL] + 10 equiv of KPF6 (upper panel right side) in acetonitrile at multiple scan
rate (mVS-1) and Differential pulse voltametric (DPV) analysis of unbound [CuL] and
[CuL]+K+(lower panel) at a scan rate of 20 mVS-1
9
Fig S14 Left Panel Cyclic voltammograms of Cu(III) couple in presence of 10 equiv of
specified redox-inactive metal ions in acetonitrile at a scan rate of 300 mVs-1 Right panel DPV
analysis of the corresponding mixtures at a scan rate of 20 mVs-1
10
Fig S15 Top UV-VIS spectra Middle CV (300 mVs-1 scan rate) and Bottom DPV (20 mVs-1 scan rate) of complex 1 at different potential range in presence of 100 equiv of TBAHFP in acetonitrile
11
Fig S16 Top UV-VIS spectra Middle CV (300 mVs-1 scan rate) and Bottom DPV (20 mVs-1 scan rate) of complex 2 at different potential range in presence of 100 equiv of TBAHFP in acetonitrile
12
Fig S17 Dependence of half-wave potentials (E12) of electrochemical reduction of the
heterometallic complexes ([(CuL)M]n+) vs pKa of M(aqua)n+ ions as measure of their Lewis
acidity
Fig S18 Electrochemical response of [CuL] in acetonitrile upon incremental addition of aquous
acetonirile (left) and the corresponding change in molar extinction coefficient of LMCT band
(right)
13
Fig S19 Electrochemical response of [CuL] + 10 eqv Zn2+ in acetonitrile upon incremental
addition of aquous acetonirile (left) and the corresponding change in molar extinction coefficient
of LMCT band (right)
Fig S20 Electrochemical response of [CuL] + 10 eqv Mg2+ in acetonitrile upon incremental
addition of aquous acetonirile (left) and the corresponding change in molar extinction coefficient
of LMCT band (right)
14
Fig S21 Correlation of shift of oxidation peak potential with equivalent of water added for
[CuL]+Mn+( Mn+ = Pr3+ Zn2+ Mg2+) (Solid line is guide for eye)
Fig S22 Correlation of change of molar absorptivity with equivalent of water added for
[CuL]+Mn+( Mn+ = Pr3+ Zn2+ Mg2+) (Solid line is guide for eye)
15
Fig S23 Correlation of the shift of oxidation peak potential with the change of molar extinction
coefficient of [CuL] in acetonitrile upon incremental addition of aquous acetonirile
Fig S24 Correlation of the shift of oxidation peak potential with the change of molar extinction
coefficient of [CuL]+10 eqv Zn2+ in acetonitrile upon incremental addition of aquous
acetonirile
16
Fig S25 Correlation of the shift of oxidation peak potential with the change of molar extinction
coefficient of [CuL]+10 eqv Mg2+ in acetonitrile upon incremental addition of aquous
acetonirile
Table S1 List of bond lengths (Aring) and bond angles (ordm) of complexes 1 and 2
M = K M = Zn
M(1)O(1) 2020(6) 2000(4)
M(1)O(2) 2179(5) 2279(5)
M(1)O(3) 2012(5) 1986(4)
M(1)O(4) 2184(6)) 2345(5)
M(1)O(5) 2058(6) 2062(5)
M(1)O(6) 2037(5) 2031(5)
Cu(1)O(1) 1920(5) 1909(5)
Cu(1)O(2) 1944(4) 1917(4)
Cu(1)N(1) 2004(6) 1982(6)
Cu(1)N(2) 1937(7) 1913(6)
Cu(2)O(3) 1909(5) 1922(5)
17
Cu(2)O(4) 1937(5) 1896(4)
Cu(2)N(3) 1966(5) 1963(5)
Cu(2)N(4) 1933(7) 1927(5)
O(1)M(1)O(2) 7448(18) 7182(17)
O(1)M(1)O(3) 1567(2) 14831(19)
O(1)M(1)O(4) 891(2) 8456(17)
O(1)M(1)O(5) 1020(2) 1061(2)
O(1)M(1)O(6) 942(2) 954(2)
O(2)M(1)O(3) 8738(19) 8400(18)
O(2)M(1)O(4) 813(2) 7719(17)
O(2)M(1)O(5) 929(2) 9441(18)
O(2)M(1)O(6) 1684(2) 16616(18)
O(3)M(1)O(4) 734(2) 7002(16)
O(3)M(1)O(5) 933(2) 9563(19)
O(3)M(1)O(6) 1028(2) 1058(2)
O(4)M(1)O(5) 1657(2) 16385(18)
O(4)M(1)O(6) 963(2) 9675(18)
O(5)M(1)O(6) 919(2) 943(2)
O(1)Cu(1)O(2) 824(2) 8238(18)
O(1)Cu(1)N(1) 905(2) 902(2)
O(1)Cu(1)N(2) 1693(3) 1690(2)
O(2)Cu(1)N(1) 1633(2) 1656(2)
O(2)Cu(1)N(2) 918(3) 920(2)
N(1)Cu(1)N(2) 974(3) 973(2)
O(2)Cu(2)O(3) 7047(16) 6993(16)
O(2)Cu(2)O(4) 684(2) 7092(17)
O(2)Cu(2)N(3) 982(2) 9683(17)
O(2)Cu(2)N(4) 1134(2) 11492(18)
18
O(3)Cu(2)O(4) 815(2) 8190(18)
O(3)Cu(2)N(3) 903(2) 901(2)
O(3)Cu(2)N(4) 1712(2) 1717(2)
O(4)Cu(2)N(3) 1660(3) 1671(2)
O(4)Cu(2)N(4) 925(3) 932(2)
N(3)Cu(2)N(4) 968(3) 959(2)
Table S2 Correlation of electrochemical response of previously reported 11 metallohost redox-inactive ion adducts derived from bicompartmental macrocyclic ligands containing adjacent N2O2 and 18-crown-6 like cavity with pKa of corresponding metal-aqua complex
[MnL](PF6)+MXn in acetonitrile MXn =
pKa E12 for Mn(IIIII) (V vs SCE)
KPF6 1625 0025LiClO4 1382 0055Ba(OTf)2 1336 0200Ca(OTf)2 1260 0245
Li+(expected)
[Li+(experimental) - Li+(expected)]
0176
0055 - 0176 =-0121
Data plotted from reference [16] of the main text
[NiL]+MXn in acetonitrileMXn =
pKa EPC for Ni(III)(V vs ferrocene)
NaPF6 1477 -165Ca(OTf)2 1260 -142Nd(OTf)3 843a -118Y(OTf)3 804a -122
Y3+(expected)
[Y3+(experimental) - Y3+(expected)]
-113
-122-(-113) =-009
aobtained from ref Data plotted from reference [17] of the main text
19
[56] of main text[CoL] + MXn in DMF MXn =
pKa E12 for Co(III)(V vs ferrocene)
K(OTf) 1625 -158Na(OTf) 1477 -158Ba(OTf)2 1336 -148Sr(OTf)2 1318 -144Ca(OTf)2 1260 -141
Na+(expected)
[Na+(experimental) - Na+(expected)]
-1515
-158 - (-1515)=-0065
Data plotted from reference [18] of the main text
[CuL]+Mn+ in DMSO Mn+=
pKa E12 for Cu(III)(V vs AgAgCl)
K+ 1625 -1277Na+ 1477 -1279Li+ 1382 -1286Ba2+ 1336 -1119Na+(expected)
[Na+(experimental) - Na+(expected)]
Li+(expected)
[Li+(experimental) - Li+(expected)]
-1185-1279-(-1185)=-0094
-1134-1286-(-1134)=-0152
Data plotted from reference [19] of the main text Line is guide for eye
[Mn(N)L] + MXn in acetonitrile MXn =
pKa E12 for Mn(VVI) (V vs ferrocene)
K(OTf) 1625 0616Na(OTf) 1477 0591Ba(OTf)2 1336 0805Sr(OTf)2 1318 0880
Na+(expected)
[Na+(experimental) - Na+(expected)]
0723
0591-0723 =-0132
Data plotted from reference [31] of the main text
20
Table S3 Masses of species obtained with their calculated values
[CuL]+ 10 eqv MXn
salts
Figure Species detected
with charge
Experimental
Mass (mz)
Calculated
Mass
(mz)
[CuL]M
[(CuL)2Li]+ 72116 72114 21Li(ClO4)3H2O S3
[(CuL)Li]+ 36407 36408 11
[(CuL)2Zn(ClO4)]+ 87701 87701 21
[(CuL)2Zn]2+ 39003 39003 21
Zn(ClO4)26H2O S4
[(CuL)Zn(ClO4)]+ 51994 51994 11
[(CuL)2Cd(ClO4)]+ 92698 92698 21
[(CuL)2Cd]2+ 41402 41401 21
Cd(ClO4)26H2O S5
[(CuL)Cd(ClO4)]+ 56991 56991 11
[(CuL)2Pr(NO3)2]+ 97903 97902 21Pr(NO3)36H2O S6
[(CuL)Pr(NO3)2]+ 62196 62196 11
[(CuL)2Nd(NO3)2]+ 98001 98001 21Nd(NO3)36H2O S7
[(CuL)Nd(NO3)2]+ 62295 62294 11
[(CuL)2Sm(NO3)2]+ 99002 99002 21Sm(NO3)36H2O S8
[(CuL)Sm(NO3)2]+ 63296 63296 11
Table S4 Comparison of HOMO-LUMO gap with the overall electrochemical shift in 11 adducts
Complex Relative stabilization of HOMO-LUMO gap (max) with
respect to [CuL]+K+
(meV)
Expected shift with respect to [CuL]+K+
1198981198901198811 119890
= 119898119881
[E12 (ox) - E12 (red)] =E12 observed from
DPV (V)
Relative shift of E12 with respect to
[CuL]+K+
(mV)
[CuL]+K+ (943-943) = 0 0466-(-1487) =1953 1953-1953 = 0
[CuL]+Na+ (4868-943) = 3925 0487-(-1412) =1899 1953-1899 = 54
[CuL]+Li+ (19920-943) = 18977 0555-(-1207) = 1762 1953-1762 = 191
[CuL]+Ca2+ (25807-943) = 24864 0589-(-1111) = 1700 1953-1700 = 253
[CuL]+Mg2+ (28543-943) = 27600 0623-(-1107) = 1730 1953-1730 = 223
21
Table S5 Summary of UV-Vis and electrochemical properties of complexes 1 and 2
Complex 1 [CuL]+10 equiv
K+
Complex 2 [CuL]+10 equiv
Zn2+
max ( LMCT) nm 3655 362 344 nm 3325
E12 (ox) (V) from
DPV
0493 0898 0466 0913 0471 0612
0920
0652 0784
E12 (red) (V) from
DPV
-1175 (hump) -
1459
-1487 -0875 (hump)
-1011 -1477
Not done
6
Fig S9 Dependence of LMCT energy bands on pKa of M(aqua)n+ ion as a measure of its Lewis acidity in presence of 100 equivalent of MprimeXn salts
Fig S10 Potential scan of unbound [CuL] and [CuL]+K+ upto first oxidation step
7
Fig S11 Left Multicycle CV of [CuL] Right CV of [CuL] at different concentration at 300 mVS scan rate in acetonitrile
Fig S12 Differential pulse voltametric (DPV) analysis of unbound [CuL] and [CuL]+K+
8
Fig S13 Cyclic voltammograms of electrochemical reduction of unbound [CuL] (upper panel
left side) and [CuL] + 10 equiv of KPF6 (upper panel right side) in acetonitrile at multiple scan
rate (mVS-1) and Differential pulse voltametric (DPV) analysis of unbound [CuL] and
[CuL]+K+(lower panel) at a scan rate of 20 mVS-1
9
Fig S14 Left Panel Cyclic voltammograms of Cu(III) couple in presence of 10 equiv of
specified redox-inactive metal ions in acetonitrile at a scan rate of 300 mVs-1 Right panel DPV
analysis of the corresponding mixtures at a scan rate of 20 mVs-1
10
Fig S15 Top UV-VIS spectra Middle CV (300 mVs-1 scan rate) and Bottom DPV (20 mVs-1 scan rate) of complex 1 at different potential range in presence of 100 equiv of TBAHFP in acetonitrile
11
Fig S16 Top UV-VIS spectra Middle CV (300 mVs-1 scan rate) and Bottom DPV (20 mVs-1 scan rate) of complex 2 at different potential range in presence of 100 equiv of TBAHFP in acetonitrile
12
Fig S17 Dependence of half-wave potentials (E12) of electrochemical reduction of the
heterometallic complexes ([(CuL)M]n+) vs pKa of M(aqua)n+ ions as measure of their Lewis
acidity
Fig S18 Electrochemical response of [CuL] in acetonitrile upon incremental addition of aquous
acetonirile (left) and the corresponding change in molar extinction coefficient of LMCT band
(right)
13
Fig S19 Electrochemical response of [CuL] + 10 eqv Zn2+ in acetonitrile upon incremental
addition of aquous acetonirile (left) and the corresponding change in molar extinction coefficient
of LMCT band (right)
Fig S20 Electrochemical response of [CuL] + 10 eqv Mg2+ in acetonitrile upon incremental
addition of aquous acetonirile (left) and the corresponding change in molar extinction coefficient
of LMCT band (right)
14
Fig S21 Correlation of shift of oxidation peak potential with equivalent of water added for
[CuL]+Mn+( Mn+ = Pr3+ Zn2+ Mg2+) (Solid line is guide for eye)
Fig S22 Correlation of change of molar absorptivity with equivalent of water added for
[CuL]+Mn+( Mn+ = Pr3+ Zn2+ Mg2+) (Solid line is guide for eye)
15
Fig S23 Correlation of the shift of oxidation peak potential with the change of molar extinction
coefficient of [CuL] in acetonitrile upon incremental addition of aquous acetonirile
Fig S24 Correlation of the shift of oxidation peak potential with the change of molar extinction
coefficient of [CuL]+10 eqv Zn2+ in acetonitrile upon incremental addition of aquous
acetonirile
16
Fig S25 Correlation of the shift of oxidation peak potential with the change of molar extinction
coefficient of [CuL]+10 eqv Mg2+ in acetonitrile upon incremental addition of aquous
acetonirile
Table S1 List of bond lengths (Aring) and bond angles (ordm) of complexes 1 and 2
M = K M = Zn
M(1)O(1) 2020(6) 2000(4)
M(1)O(2) 2179(5) 2279(5)
M(1)O(3) 2012(5) 1986(4)
M(1)O(4) 2184(6)) 2345(5)
M(1)O(5) 2058(6) 2062(5)
M(1)O(6) 2037(5) 2031(5)
Cu(1)O(1) 1920(5) 1909(5)
Cu(1)O(2) 1944(4) 1917(4)
Cu(1)N(1) 2004(6) 1982(6)
Cu(1)N(2) 1937(7) 1913(6)
Cu(2)O(3) 1909(5) 1922(5)
17
Cu(2)O(4) 1937(5) 1896(4)
Cu(2)N(3) 1966(5) 1963(5)
Cu(2)N(4) 1933(7) 1927(5)
O(1)M(1)O(2) 7448(18) 7182(17)
O(1)M(1)O(3) 1567(2) 14831(19)
O(1)M(1)O(4) 891(2) 8456(17)
O(1)M(1)O(5) 1020(2) 1061(2)
O(1)M(1)O(6) 942(2) 954(2)
O(2)M(1)O(3) 8738(19) 8400(18)
O(2)M(1)O(4) 813(2) 7719(17)
O(2)M(1)O(5) 929(2) 9441(18)
O(2)M(1)O(6) 1684(2) 16616(18)
O(3)M(1)O(4) 734(2) 7002(16)
O(3)M(1)O(5) 933(2) 9563(19)
O(3)M(1)O(6) 1028(2) 1058(2)
O(4)M(1)O(5) 1657(2) 16385(18)
O(4)M(1)O(6) 963(2) 9675(18)
O(5)M(1)O(6) 919(2) 943(2)
O(1)Cu(1)O(2) 824(2) 8238(18)
O(1)Cu(1)N(1) 905(2) 902(2)
O(1)Cu(1)N(2) 1693(3) 1690(2)
O(2)Cu(1)N(1) 1633(2) 1656(2)
O(2)Cu(1)N(2) 918(3) 920(2)
N(1)Cu(1)N(2) 974(3) 973(2)
O(2)Cu(2)O(3) 7047(16) 6993(16)
O(2)Cu(2)O(4) 684(2) 7092(17)
O(2)Cu(2)N(3) 982(2) 9683(17)
O(2)Cu(2)N(4) 1134(2) 11492(18)
18
O(3)Cu(2)O(4) 815(2) 8190(18)
O(3)Cu(2)N(3) 903(2) 901(2)
O(3)Cu(2)N(4) 1712(2) 1717(2)
O(4)Cu(2)N(3) 1660(3) 1671(2)
O(4)Cu(2)N(4) 925(3) 932(2)
N(3)Cu(2)N(4) 968(3) 959(2)
Table S2 Correlation of electrochemical response of previously reported 11 metallohost redox-inactive ion adducts derived from bicompartmental macrocyclic ligands containing adjacent N2O2 and 18-crown-6 like cavity with pKa of corresponding metal-aqua complex
[MnL](PF6)+MXn in acetonitrile MXn =
pKa E12 for Mn(IIIII) (V vs SCE)
KPF6 1625 0025LiClO4 1382 0055Ba(OTf)2 1336 0200Ca(OTf)2 1260 0245
Li+(expected)
[Li+(experimental) - Li+(expected)]
0176
0055 - 0176 =-0121
Data plotted from reference [16] of the main text
[NiL]+MXn in acetonitrileMXn =
pKa EPC for Ni(III)(V vs ferrocene)
NaPF6 1477 -165Ca(OTf)2 1260 -142Nd(OTf)3 843a -118Y(OTf)3 804a -122
Y3+(expected)
[Y3+(experimental) - Y3+(expected)]
-113
-122-(-113) =-009
aobtained from ref Data plotted from reference [17] of the main text
19
[56] of main text[CoL] + MXn in DMF MXn =
pKa E12 for Co(III)(V vs ferrocene)
K(OTf) 1625 -158Na(OTf) 1477 -158Ba(OTf)2 1336 -148Sr(OTf)2 1318 -144Ca(OTf)2 1260 -141
Na+(expected)
[Na+(experimental) - Na+(expected)]
-1515
-158 - (-1515)=-0065
Data plotted from reference [18] of the main text
[CuL]+Mn+ in DMSO Mn+=
pKa E12 for Cu(III)(V vs AgAgCl)
K+ 1625 -1277Na+ 1477 -1279Li+ 1382 -1286Ba2+ 1336 -1119Na+(expected)
[Na+(experimental) - Na+(expected)]
Li+(expected)
[Li+(experimental) - Li+(expected)]
-1185-1279-(-1185)=-0094
-1134-1286-(-1134)=-0152
Data plotted from reference [19] of the main text Line is guide for eye
[Mn(N)L] + MXn in acetonitrile MXn =
pKa E12 for Mn(VVI) (V vs ferrocene)
K(OTf) 1625 0616Na(OTf) 1477 0591Ba(OTf)2 1336 0805Sr(OTf)2 1318 0880
Na+(expected)
[Na+(experimental) - Na+(expected)]
0723
0591-0723 =-0132
Data plotted from reference [31] of the main text
20
Table S3 Masses of species obtained with their calculated values
[CuL]+ 10 eqv MXn
salts
Figure Species detected
with charge
Experimental
Mass (mz)
Calculated
Mass
(mz)
[CuL]M
[(CuL)2Li]+ 72116 72114 21Li(ClO4)3H2O S3
[(CuL)Li]+ 36407 36408 11
[(CuL)2Zn(ClO4)]+ 87701 87701 21
[(CuL)2Zn]2+ 39003 39003 21
Zn(ClO4)26H2O S4
[(CuL)Zn(ClO4)]+ 51994 51994 11
[(CuL)2Cd(ClO4)]+ 92698 92698 21
[(CuL)2Cd]2+ 41402 41401 21
Cd(ClO4)26H2O S5
[(CuL)Cd(ClO4)]+ 56991 56991 11
[(CuL)2Pr(NO3)2]+ 97903 97902 21Pr(NO3)36H2O S6
[(CuL)Pr(NO3)2]+ 62196 62196 11
[(CuL)2Nd(NO3)2]+ 98001 98001 21Nd(NO3)36H2O S7
[(CuL)Nd(NO3)2]+ 62295 62294 11
[(CuL)2Sm(NO3)2]+ 99002 99002 21Sm(NO3)36H2O S8
[(CuL)Sm(NO3)2]+ 63296 63296 11
Table S4 Comparison of HOMO-LUMO gap with the overall electrochemical shift in 11 adducts
Complex Relative stabilization of HOMO-LUMO gap (max) with
respect to [CuL]+K+
(meV)
Expected shift with respect to [CuL]+K+
1198981198901198811 119890
= 119898119881
[E12 (ox) - E12 (red)] =E12 observed from
DPV (V)
Relative shift of E12 with respect to
[CuL]+K+
(mV)
[CuL]+K+ (943-943) = 0 0466-(-1487) =1953 1953-1953 = 0
[CuL]+Na+ (4868-943) = 3925 0487-(-1412) =1899 1953-1899 = 54
[CuL]+Li+ (19920-943) = 18977 0555-(-1207) = 1762 1953-1762 = 191
[CuL]+Ca2+ (25807-943) = 24864 0589-(-1111) = 1700 1953-1700 = 253
[CuL]+Mg2+ (28543-943) = 27600 0623-(-1107) = 1730 1953-1730 = 223
21
Table S5 Summary of UV-Vis and electrochemical properties of complexes 1 and 2
Complex 1 [CuL]+10 equiv
K+
Complex 2 [CuL]+10 equiv
Zn2+
max ( LMCT) nm 3655 362 344 nm 3325
E12 (ox) (V) from
DPV
0493 0898 0466 0913 0471 0612
0920
0652 0784
E12 (red) (V) from
DPV
-1175 (hump) -
1459
-1487 -0875 (hump)
-1011 -1477
Not done
7
Fig S11 Left Multicycle CV of [CuL] Right CV of [CuL] at different concentration at 300 mVS scan rate in acetonitrile
Fig S12 Differential pulse voltametric (DPV) analysis of unbound [CuL] and [CuL]+K+
8
Fig S13 Cyclic voltammograms of electrochemical reduction of unbound [CuL] (upper panel
left side) and [CuL] + 10 equiv of KPF6 (upper panel right side) in acetonitrile at multiple scan
rate (mVS-1) and Differential pulse voltametric (DPV) analysis of unbound [CuL] and
[CuL]+K+(lower panel) at a scan rate of 20 mVS-1
9
Fig S14 Left Panel Cyclic voltammograms of Cu(III) couple in presence of 10 equiv of
specified redox-inactive metal ions in acetonitrile at a scan rate of 300 mVs-1 Right panel DPV
analysis of the corresponding mixtures at a scan rate of 20 mVs-1
10
Fig S15 Top UV-VIS spectra Middle CV (300 mVs-1 scan rate) and Bottom DPV (20 mVs-1 scan rate) of complex 1 at different potential range in presence of 100 equiv of TBAHFP in acetonitrile
11
Fig S16 Top UV-VIS spectra Middle CV (300 mVs-1 scan rate) and Bottom DPV (20 mVs-1 scan rate) of complex 2 at different potential range in presence of 100 equiv of TBAHFP in acetonitrile
12
Fig S17 Dependence of half-wave potentials (E12) of electrochemical reduction of the
heterometallic complexes ([(CuL)M]n+) vs pKa of M(aqua)n+ ions as measure of their Lewis
acidity
Fig S18 Electrochemical response of [CuL] in acetonitrile upon incremental addition of aquous
acetonirile (left) and the corresponding change in molar extinction coefficient of LMCT band
(right)
13
Fig S19 Electrochemical response of [CuL] + 10 eqv Zn2+ in acetonitrile upon incremental
addition of aquous acetonirile (left) and the corresponding change in molar extinction coefficient
of LMCT band (right)
Fig S20 Electrochemical response of [CuL] + 10 eqv Mg2+ in acetonitrile upon incremental
addition of aquous acetonirile (left) and the corresponding change in molar extinction coefficient
of LMCT band (right)
14
Fig S21 Correlation of shift of oxidation peak potential with equivalent of water added for
[CuL]+Mn+( Mn+ = Pr3+ Zn2+ Mg2+) (Solid line is guide for eye)
Fig S22 Correlation of change of molar absorptivity with equivalent of water added for
[CuL]+Mn+( Mn+ = Pr3+ Zn2+ Mg2+) (Solid line is guide for eye)
15
Fig S23 Correlation of the shift of oxidation peak potential with the change of molar extinction
coefficient of [CuL] in acetonitrile upon incremental addition of aquous acetonirile
Fig S24 Correlation of the shift of oxidation peak potential with the change of molar extinction
coefficient of [CuL]+10 eqv Zn2+ in acetonitrile upon incremental addition of aquous
acetonirile
16
Fig S25 Correlation of the shift of oxidation peak potential with the change of molar extinction
coefficient of [CuL]+10 eqv Mg2+ in acetonitrile upon incremental addition of aquous
acetonirile
Table S1 List of bond lengths (Aring) and bond angles (ordm) of complexes 1 and 2
M = K M = Zn
M(1)O(1) 2020(6) 2000(4)
M(1)O(2) 2179(5) 2279(5)
M(1)O(3) 2012(5) 1986(4)
M(1)O(4) 2184(6)) 2345(5)
M(1)O(5) 2058(6) 2062(5)
M(1)O(6) 2037(5) 2031(5)
Cu(1)O(1) 1920(5) 1909(5)
Cu(1)O(2) 1944(4) 1917(4)
Cu(1)N(1) 2004(6) 1982(6)
Cu(1)N(2) 1937(7) 1913(6)
Cu(2)O(3) 1909(5) 1922(5)
17
Cu(2)O(4) 1937(5) 1896(4)
Cu(2)N(3) 1966(5) 1963(5)
Cu(2)N(4) 1933(7) 1927(5)
O(1)M(1)O(2) 7448(18) 7182(17)
O(1)M(1)O(3) 1567(2) 14831(19)
O(1)M(1)O(4) 891(2) 8456(17)
O(1)M(1)O(5) 1020(2) 1061(2)
O(1)M(1)O(6) 942(2) 954(2)
O(2)M(1)O(3) 8738(19) 8400(18)
O(2)M(1)O(4) 813(2) 7719(17)
O(2)M(1)O(5) 929(2) 9441(18)
O(2)M(1)O(6) 1684(2) 16616(18)
O(3)M(1)O(4) 734(2) 7002(16)
O(3)M(1)O(5) 933(2) 9563(19)
O(3)M(1)O(6) 1028(2) 1058(2)
O(4)M(1)O(5) 1657(2) 16385(18)
O(4)M(1)O(6) 963(2) 9675(18)
O(5)M(1)O(6) 919(2) 943(2)
O(1)Cu(1)O(2) 824(2) 8238(18)
O(1)Cu(1)N(1) 905(2) 902(2)
O(1)Cu(1)N(2) 1693(3) 1690(2)
O(2)Cu(1)N(1) 1633(2) 1656(2)
O(2)Cu(1)N(2) 918(3) 920(2)
N(1)Cu(1)N(2) 974(3) 973(2)
O(2)Cu(2)O(3) 7047(16) 6993(16)
O(2)Cu(2)O(4) 684(2) 7092(17)
O(2)Cu(2)N(3) 982(2) 9683(17)
O(2)Cu(2)N(4) 1134(2) 11492(18)
18
O(3)Cu(2)O(4) 815(2) 8190(18)
O(3)Cu(2)N(3) 903(2) 901(2)
O(3)Cu(2)N(4) 1712(2) 1717(2)
O(4)Cu(2)N(3) 1660(3) 1671(2)
O(4)Cu(2)N(4) 925(3) 932(2)
N(3)Cu(2)N(4) 968(3) 959(2)
Table S2 Correlation of electrochemical response of previously reported 11 metallohost redox-inactive ion adducts derived from bicompartmental macrocyclic ligands containing adjacent N2O2 and 18-crown-6 like cavity with pKa of corresponding metal-aqua complex
[MnL](PF6)+MXn in acetonitrile MXn =
pKa E12 for Mn(IIIII) (V vs SCE)
KPF6 1625 0025LiClO4 1382 0055Ba(OTf)2 1336 0200Ca(OTf)2 1260 0245
Li+(expected)
[Li+(experimental) - Li+(expected)]
0176
0055 - 0176 =-0121
Data plotted from reference [16] of the main text
[NiL]+MXn in acetonitrileMXn =
pKa EPC for Ni(III)(V vs ferrocene)
NaPF6 1477 -165Ca(OTf)2 1260 -142Nd(OTf)3 843a -118Y(OTf)3 804a -122
Y3+(expected)
[Y3+(experimental) - Y3+(expected)]
-113
-122-(-113) =-009
aobtained from ref Data plotted from reference [17] of the main text
19
[56] of main text[CoL] + MXn in DMF MXn =
pKa E12 for Co(III)(V vs ferrocene)
K(OTf) 1625 -158Na(OTf) 1477 -158Ba(OTf)2 1336 -148Sr(OTf)2 1318 -144Ca(OTf)2 1260 -141
Na+(expected)
[Na+(experimental) - Na+(expected)]
-1515
-158 - (-1515)=-0065
Data plotted from reference [18] of the main text
[CuL]+Mn+ in DMSO Mn+=
pKa E12 for Cu(III)(V vs AgAgCl)
K+ 1625 -1277Na+ 1477 -1279Li+ 1382 -1286Ba2+ 1336 -1119Na+(expected)
[Na+(experimental) - Na+(expected)]
Li+(expected)
[Li+(experimental) - Li+(expected)]
-1185-1279-(-1185)=-0094
-1134-1286-(-1134)=-0152
Data plotted from reference [19] of the main text Line is guide for eye
[Mn(N)L] + MXn in acetonitrile MXn =
pKa E12 for Mn(VVI) (V vs ferrocene)
K(OTf) 1625 0616Na(OTf) 1477 0591Ba(OTf)2 1336 0805Sr(OTf)2 1318 0880
Na+(expected)
[Na+(experimental) - Na+(expected)]
0723
0591-0723 =-0132
Data plotted from reference [31] of the main text
20
Table S3 Masses of species obtained with their calculated values
[CuL]+ 10 eqv MXn
salts
Figure Species detected
with charge
Experimental
Mass (mz)
Calculated
Mass
(mz)
[CuL]M
[(CuL)2Li]+ 72116 72114 21Li(ClO4)3H2O S3
[(CuL)Li]+ 36407 36408 11
[(CuL)2Zn(ClO4)]+ 87701 87701 21
[(CuL)2Zn]2+ 39003 39003 21
Zn(ClO4)26H2O S4
[(CuL)Zn(ClO4)]+ 51994 51994 11
[(CuL)2Cd(ClO4)]+ 92698 92698 21
[(CuL)2Cd]2+ 41402 41401 21
Cd(ClO4)26H2O S5
[(CuL)Cd(ClO4)]+ 56991 56991 11
[(CuL)2Pr(NO3)2]+ 97903 97902 21Pr(NO3)36H2O S6
[(CuL)Pr(NO3)2]+ 62196 62196 11
[(CuL)2Nd(NO3)2]+ 98001 98001 21Nd(NO3)36H2O S7
[(CuL)Nd(NO3)2]+ 62295 62294 11
[(CuL)2Sm(NO3)2]+ 99002 99002 21Sm(NO3)36H2O S8
[(CuL)Sm(NO3)2]+ 63296 63296 11
Table S4 Comparison of HOMO-LUMO gap with the overall electrochemical shift in 11 adducts
Complex Relative stabilization of HOMO-LUMO gap (max) with
respect to [CuL]+K+
(meV)
Expected shift with respect to [CuL]+K+
1198981198901198811 119890
= 119898119881
[E12 (ox) - E12 (red)] =E12 observed from
DPV (V)
Relative shift of E12 with respect to
[CuL]+K+
(mV)
[CuL]+K+ (943-943) = 0 0466-(-1487) =1953 1953-1953 = 0
[CuL]+Na+ (4868-943) = 3925 0487-(-1412) =1899 1953-1899 = 54
[CuL]+Li+ (19920-943) = 18977 0555-(-1207) = 1762 1953-1762 = 191
[CuL]+Ca2+ (25807-943) = 24864 0589-(-1111) = 1700 1953-1700 = 253
[CuL]+Mg2+ (28543-943) = 27600 0623-(-1107) = 1730 1953-1730 = 223
21
Table S5 Summary of UV-Vis and electrochemical properties of complexes 1 and 2
Complex 1 [CuL]+10 equiv
K+
Complex 2 [CuL]+10 equiv
Zn2+
max ( LMCT) nm 3655 362 344 nm 3325
E12 (ox) (V) from
DPV
0493 0898 0466 0913 0471 0612
0920
0652 0784
E12 (red) (V) from
DPV
-1175 (hump) -
1459
-1487 -0875 (hump)
-1011 -1477
Not done
8
Fig S13 Cyclic voltammograms of electrochemical reduction of unbound [CuL] (upper panel
left side) and [CuL] + 10 equiv of KPF6 (upper panel right side) in acetonitrile at multiple scan
rate (mVS-1) and Differential pulse voltametric (DPV) analysis of unbound [CuL] and
[CuL]+K+(lower panel) at a scan rate of 20 mVS-1
9
Fig S14 Left Panel Cyclic voltammograms of Cu(III) couple in presence of 10 equiv of
specified redox-inactive metal ions in acetonitrile at a scan rate of 300 mVs-1 Right panel DPV
analysis of the corresponding mixtures at a scan rate of 20 mVs-1
10
Fig S15 Top UV-VIS spectra Middle CV (300 mVs-1 scan rate) and Bottom DPV (20 mVs-1 scan rate) of complex 1 at different potential range in presence of 100 equiv of TBAHFP in acetonitrile
11
Fig S16 Top UV-VIS spectra Middle CV (300 mVs-1 scan rate) and Bottom DPV (20 mVs-1 scan rate) of complex 2 at different potential range in presence of 100 equiv of TBAHFP in acetonitrile
12
Fig S17 Dependence of half-wave potentials (E12) of electrochemical reduction of the
heterometallic complexes ([(CuL)M]n+) vs pKa of M(aqua)n+ ions as measure of their Lewis
acidity
Fig S18 Electrochemical response of [CuL] in acetonitrile upon incremental addition of aquous
acetonirile (left) and the corresponding change in molar extinction coefficient of LMCT band
(right)
13
Fig S19 Electrochemical response of [CuL] + 10 eqv Zn2+ in acetonitrile upon incremental
addition of aquous acetonirile (left) and the corresponding change in molar extinction coefficient
of LMCT band (right)
Fig S20 Electrochemical response of [CuL] + 10 eqv Mg2+ in acetonitrile upon incremental
addition of aquous acetonirile (left) and the corresponding change in molar extinction coefficient
of LMCT band (right)
14
Fig S21 Correlation of shift of oxidation peak potential with equivalent of water added for
[CuL]+Mn+( Mn+ = Pr3+ Zn2+ Mg2+) (Solid line is guide for eye)
Fig S22 Correlation of change of molar absorptivity with equivalent of water added for
[CuL]+Mn+( Mn+ = Pr3+ Zn2+ Mg2+) (Solid line is guide for eye)
15
Fig S23 Correlation of the shift of oxidation peak potential with the change of molar extinction
coefficient of [CuL] in acetonitrile upon incremental addition of aquous acetonirile
Fig S24 Correlation of the shift of oxidation peak potential with the change of molar extinction
coefficient of [CuL]+10 eqv Zn2+ in acetonitrile upon incremental addition of aquous
acetonirile
16
Fig S25 Correlation of the shift of oxidation peak potential with the change of molar extinction
coefficient of [CuL]+10 eqv Mg2+ in acetonitrile upon incremental addition of aquous
acetonirile
Table S1 List of bond lengths (Aring) and bond angles (ordm) of complexes 1 and 2
M = K M = Zn
M(1)O(1) 2020(6) 2000(4)
M(1)O(2) 2179(5) 2279(5)
M(1)O(3) 2012(5) 1986(4)
M(1)O(4) 2184(6)) 2345(5)
M(1)O(5) 2058(6) 2062(5)
M(1)O(6) 2037(5) 2031(5)
Cu(1)O(1) 1920(5) 1909(5)
Cu(1)O(2) 1944(4) 1917(4)
Cu(1)N(1) 2004(6) 1982(6)
Cu(1)N(2) 1937(7) 1913(6)
Cu(2)O(3) 1909(5) 1922(5)
17
Cu(2)O(4) 1937(5) 1896(4)
Cu(2)N(3) 1966(5) 1963(5)
Cu(2)N(4) 1933(7) 1927(5)
O(1)M(1)O(2) 7448(18) 7182(17)
O(1)M(1)O(3) 1567(2) 14831(19)
O(1)M(1)O(4) 891(2) 8456(17)
O(1)M(1)O(5) 1020(2) 1061(2)
O(1)M(1)O(6) 942(2) 954(2)
O(2)M(1)O(3) 8738(19) 8400(18)
O(2)M(1)O(4) 813(2) 7719(17)
O(2)M(1)O(5) 929(2) 9441(18)
O(2)M(1)O(6) 1684(2) 16616(18)
O(3)M(1)O(4) 734(2) 7002(16)
O(3)M(1)O(5) 933(2) 9563(19)
O(3)M(1)O(6) 1028(2) 1058(2)
O(4)M(1)O(5) 1657(2) 16385(18)
O(4)M(1)O(6) 963(2) 9675(18)
O(5)M(1)O(6) 919(2) 943(2)
O(1)Cu(1)O(2) 824(2) 8238(18)
O(1)Cu(1)N(1) 905(2) 902(2)
O(1)Cu(1)N(2) 1693(3) 1690(2)
O(2)Cu(1)N(1) 1633(2) 1656(2)
O(2)Cu(1)N(2) 918(3) 920(2)
N(1)Cu(1)N(2) 974(3) 973(2)
O(2)Cu(2)O(3) 7047(16) 6993(16)
O(2)Cu(2)O(4) 684(2) 7092(17)
O(2)Cu(2)N(3) 982(2) 9683(17)
O(2)Cu(2)N(4) 1134(2) 11492(18)
18
O(3)Cu(2)O(4) 815(2) 8190(18)
O(3)Cu(2)N(3) 903(2) 901(2)
O(3)Cu(2)N(4) 1712(2) 1717(2)
O(4)Cu(2)N(3) 1660(3) 1671(2)
O(4)Cu(2)N(4) 925(3) 932(2)
N(3)Cu(2)N(4) 968(3) 959(2)
Table S2 Correlation of electrochemical response of previously reported 11 metallohost redox-inactive ion adducts derived from bicompartmental macrocyclic ligands containing adjacent N2O2 and 18-crown-6 like cavity with pKa of corresponding metal-aqua complex
[MnL](PF6)+MXn in acetonitrile MXn =
pKa E12 for Mn(IIIII) (V vs SCE)
KPF6 1625 0025LiClO4 1382 0055Ba(OTf)2 1336 0200Ca(OTf)2 1260 0245
Li+(expected)
[Li+(experimental) - Li+(expected)]
0176
0055 - 0176 =-0121
Data plotted from reference [16] of the main text
[NiL]+MXn in acetonitrileMXn =
pKa EPC for Ni(III)(V vs ferrocene)
NaPF6 1477 -165Ca(OTf)2 1260 -142Nd(OTf)3 843a -118Y(OTf)3 804a -122
Y3+(expected)
[Y3+(experimental) - Y3+(expected)]
-113
-122-(-113) =-009
aobtained from ref Data plotted from reference [17] of the main text
19
[56] of main text[CoL] + MXn in DMF MXn =
pKa E12 for Co(III)(V vs ferrocene)
K(OTf) 1625 -158Na(OTf) 1477 -158Ba(OTf)2 1336 -148Sr(OTf)2 1318 -144Ca(OTf)2 1260 -141
Na+(expected)
[Na+(experimental) - Na+(expected)]
-1515
-158 - (-1515)=-0065
Data plotted from reference [18] of the main text
[CuL]+Mn+ in DMSO Mn+=
pKa E12 for Cu(III)(V vs AgAgCl)
K+ 1625 -1277Na+ 1477 -1279Li+ 1382 -1286Ba2+ 1336 -1119Na+(expected)
[Na+(experimental) - Na+(expected)]
Li+(expected)
[Li+(experimental) - Li+(expected)]
-1185-1279-(-1185)=-0094
-1134-1286-(-1134)=-0152
Data plotted from reference [19] of the main text Line is guide for eye
[Mn(N)L] + MXn in acetonitrile MXn =
pKa E12 for Mn(VVI) (V vs ferrocene)
K(OTf) 1625 0616Na(OTf) 1477 0591Ba(OTf)2 1336 0805Sr(OTf)2 1318 0880
Na+(expected)
[Na+(experimental) - Na+(expected)]
0723
0591-0723 =-0132
Data plotted from reference [31] of the main text
20
Table S3 Masses of species obtained with their calculated values
[CuL]+ 10 eqv MXn
salts
Figure Species detected
with charge
Experimental
Mass (mz)
Calculated
Mass
(mz)
[CuL]M
[(CuL)2Li]+ 72116 72114 21Li(ClO4)3H2O S3
[(CuL)Li]+ 36407 36408 11
[(CuL)2Zn(ClO4)]+ 87701 87701 21
[(CuL)2Zn]2+ 39003 39003 21
Zn(ClO4)26H2O S4
[(CuL)Zn(ClO4)]+ 51994 51994 11
[(CuL)2Cd(ClO4)]+ 92698 92698 21
[(CuL)2Cd]2+ 41402 41401 21
Cd(ClO4)26H2O S5
[(CuL)Cd(ClO4)]+ 56991 56991 11
[(CuL)2Pr(NO3)2]+ 97903 97902 21Pr(NO3)36H2O S6
[(CuL)Pr(NO3)2]+ 62196 62196 11
[(CuL)2Nd(NO3)2]+ 98001 98001 21Nd(NO3)36H2O S7
[(CuL)Nd(NO3)2]+ 62295 62294 11
[(CuL)2Sm(NO3)2]+ 99002 99002 21Sm(NO3)36H2O S8
[(CuL)Sm(NO3)2]+ 63296 63296 11
Table S4 Comparison of HOMO-LUMO gap with the overall electrochemical shift in 11 adducts
Complex Relative stabilization of HOMO-LUMO gap (max) with
respect to [CuL]+K+
(meV)
Expected shift with respect to [CuL]+K+
1198981198901198811 119890
= 119898119881
[E12 (ox) - E12 (red)] =E12 observed from
DPV (V)
Relative shift of E12 with respect to
[CuL]+K+
(mV)
[CuL]+K+ (943-943) = 0 0466-(-1487) =1953 1953-1953 = 0
[CuL]+Na+ (4868-943) = 3925 0487-(-1412) =1899 1953-1899 = 54
[CuL]+Li+ (19920-943) = 18977 0555-(-1207) = 1762 1953-1762 = 191
[CuL]+Ca2+ (25807-943) = 24864 0589-(-1111) = 1700 1953-1700 = 253
[CuL]+Mg2+ (28543-943) = 27600 0623-(-1107) = 1730 1953-1730 = 223
21
Table S5 Summary of UV-Vis and electrochemical properties of complexes 1 and 2
Complex 1 [CuL]+10 equiv
K+
Complex 2 [CuL]+10 equiv
Zn2+
max ( LMCT) nm 3655 362 344 nm 3325
E12 (ox) (V) from
DPV
0493 0898 0466 0913 0471 0612
0920
0652 0784
E12 (red) (V) from
DPV
-1175 (hump) -
1459
-1487 -0875 (hump)
-1011 -1477
Not done
9
Fig S14 Left Panel Cyclic voltammograms of Cu(III) couple in presence of 10 equiv of
specified redox-inactive metal ions in acetonitrile at a scan rate of 300 mVs-1 Right panel DPV
analysis of the corresponding mixtures at a scan rate of 20 mVs-1
10
Fig S15 Top UV-VIS spectra Middle CV (300 mVs-1 scan rate) and Bottom DPV (20 mVs-1 scan rate) of complex 1 at different potential range in presence of 100 equiv of TBAHFP in acetonitrile
11
Fig S16 Top UV-VIS spectra Middle CV (300 mVs-1 scan rate) and Bottom DPV (20 mVs-1 scan rate) of complex 2 at different potential range in presence of 100 equiv of TBAHFP in acetonitrile
12
Fig S17 Dependence of half-wave potentials (E12) of electrochemical reduction of the
heterometallic complexes ([(CuL)M]n+) vs pKa of M(aqua)n+ ions as measure of their Lewis
acidity
Fig S18 Electrochemical response of [CuL] in acetonitrile upon incremental addition of aquous
acetonirile (left) and the corresponding change in molar extinction coefficient of LMCT band
(right)
13
Fig S19 Electrochemical response of [CuL] + 10 eqv Zn2+ in acetonitrile upon incremental
addition of aquous acetonirile (left) and the corresponding change in molar extinction coefficient
of LMCT band (right)
Fig S20 Electrochemical response of [CuL] + 10 eqv Mg2+ in acetonitrile upon incremental
addition of aquous acetonirile (left) and the corresponding change in molar extinction coefficient
of LMCT band (right)
14
Fig S21 Correlation of shift of oxidation peak potential with equivalent of water added for
[CuL]+Mn+( Mn+ = Pr3+ Zn2+ Mg2+) (Solid line is guide for eye)
Fig S22 Correlation of change of molar absorptivity with equivalent of water added for
[CuL]+Mn+( Mn+ = Pr3+ Zn2+ Mg2+) (Solid line is guide for eye)
15
Fig S23 Correlation of the shift of oxidation peak potential with the change of molar extinction
coefficient of [CuL] in acetonitrile upon incremental addition of aquous acetonirile
Fig S24 Correlation of the shift of oxidation peak potential with the change of molar extinction
coefficient of [CuL]+10 eqv Zn2+ in acetonitrile upon incremental addition of aquous
acetonirile
16
Fig S25 Correlation of the shift of oxidation peak potential with the change of molar extinction
coefficient of [CuL]+10 eqv Mg2+ in acetonitrile upon incremental addition of aquous
acetonirile
Table S1 List of bond lengths (Aring) and bond angles (ordm) of complexes 1 and 2
M = K M = Zn
M(1)O(1) 2020(6) 2000(4)
M(1)O(2) 2179(5) 2279(5)
M(1)O(3) 2012(5) 1986(4)
M(1)O(4) 2184(6)) 2345(5)
M(1)O(5) 2058(6) 2062(5)
M(1)O(6) 2037(5) 2031(5)
Cu(1)O(1) 1920(5) 1909(5)
Cu(1)O(2) 1944(4) 1917(4)
Cu(1)N(1) 2004(6) 1982(6)
Cu(1)N(2) 1937(7) 1913(6)
Cu(2)O(3) 1909(5) 1922(5)
17
Cu(2)O(4) 1937(5) 1896(4)
Cu(2)N(3) 1966(5) 1963(5)
Cu(2)N(4) 1933(7) 1927(5)
O(1)M(1)O(2) 7448(18) 7182(17)
O(1)M(1)O(3) 1567(2) 14831(19)
O(1)M(1)O(4) 891(2) 8456(17)
O(1)M(1)O(5) 1020(2) 1061(2)
O(1)M(1)O(6) 942(2) 954(2)
O(2)M(1)O(3) 8738(19) 8400(18)
O(2)M(1)O(4) 813(2) 7719(17)
O(2)M(1)O(5) 929(2) 9441(18)
O(2)M(1)O(6) 1684(2) 16616(18)
O(3)M(1)O(4) 734(2) 7002(16)
O(3)M(1)O(5) 933(2) 9563(19)
O(3)M(1)O(6) 1028(2) 1058(2)
O(4)M(1)O(5) 1657(2) 16385(18)
O(4)M(1)O(6) 963(2) 9675(18)
O(5)M(1)O(6) 919(2) 943(2)
O(1)Cu(1)O(2) 824(2) 8238(18)
O(1)Cu(1)N(1) 905(2) 902(2)
O(1)Cu(1)N(2) 1693(3) 1690(2)
O(2)Cu(1)N(1) 1633(2) 1656(2)
O(2)Cu(1)N(2) 918(3) 920(2)
N(1)Cu(1)N(2) 974(3) 973(2)
O(2)Cu(2)O(3) 7047(16) 6993(16)
O(2)Cu(2)O(4) 684(2) 7092(17)
O(2)Cu(2)N(3) 982(2) 9683(17)
O(2)Cu(2)N(4) 1134(2) 11492(18)
18
O(3)Cu(2)O(4) 815(2) 8190(18)
O(3)Cu(2)N(3) 903(2) 901(2)
O(3)Cu(2)N(4) 1712(2) 1717(2)
O(4)Cu(2)N(3) 1660(3) 1671(2)
O(4)Cu(2)N(4) 925(3) 932(2)
N(3)Cu(2)N(4) 968(3) 959(2)
Table S2 Correlation of electrochemical response of previously reported 11 metallohost redox-inactive ion adducts derived from bicompartmental macrocyclic ligands containing adjacent N2O2 and 18-crown-6 like cavity with pKa of corresponding metal-aqua complex
[MnL](PF6)+MXn in acetonitrile MXn =
pKa E12 for Mn(IIIII) (V vs SCE)
KPF6 1625 0025LiClO4 1382 0055Ba(OTf)2 1336 0200Ca(OTf)2 1260 0245
Li+(expected)
[Li+(experimental) - Li+(expected)]
0176
0055 - 0176 =-0121
Data plotted from reference [16] of the main text
[NiL]+MXn in acetonitrileMXn =
pKa EPC for Ni(III)(V vs ferrocene)
NaPF6 1477 -165Ca(OTf)2 1260 -142Nd(OTf)3 843a -118Y(OTf)3 804a -122
Y3+(expected)
[Y3+(experimental) - Y3+(expected)]
-113
-122-(-113) =-009
aobtained from ref Data plotted from reference [17] of the main text
19
[56] of main text[CoL] + MXn in DMF MXn =
pKa E12 for Co(III)(V vs ferrocene)
K(OTf) 1625 -158Na(OTf) 1477 -158Ba(OTf)2 1336 -148Sr(OTf)2 1318 -144Ca(OTf)2 1260 -141
Na+(expected)
[Na+(experimental) - Na+(expected)]
-1515
-158 - (-1515)=-0065
Data plotted from reference [18] of the main text
[CuL]+Mn+ in DMSO Mn+=
pKa E12 for Cu(III)(V vs AgAgCl)
K+ 1625 -1277Na+ 1477 -1279Li+ 1382 -1286Ba2+ 1336 -1119Na+(expected)
[Na+(experimental) - Na+(expected)]
Li+(expected)
[Li+(experimental) - Li+(expected)]
-1185-1279-(-1185)=-0094
-1134-1286-(-1134)=-0152
Data plotted from reference [19] of the main text Line is guide for eye
[Mn(N)L] + MXn in acetonitrile MXn =
pKa E12 for Mn(VVI) (V vs ferrocene)
K(OTf) 1625 0616Na(OTf) 1477 0591Ba(OTf)2 1336 0805Sr(OTf)2 1318 0880
Na+(expected)
[Na+(experimental) - Na+(expected)]
0723
0591-0723 =-0132
Data plotted from reference [31] of the main text
20
Table S3 Masses of species obtained with their calculated values
[CuL]+ 10 eqv MXn
salts
Figure Species detected
with charge
Experimental
Mass (mz)
Calculated
Mass
(mz)
[CuL]M
[(CuL)2Li]+ 72116 72114 21Li(ClO4)3H2O S3
[(CuL)Li]+ 36407 36408 11
[(CuL)2Zn(ClO4)]+ 87701 87701 21
[(CuL)2Zn]2+ 39003 39003 21
Zn(ClO4)26H2O S4
[(CuL)Zn(ClO4)]+ 51994 51994 11
[(CuL)2Cd(ClO4)]+ 92698 92698 21
[(CuL)2Cd]2+ 41402 41401 21
Cd(ClO4)26H2O S5
[(CuL)Cd(ClO4)]+ 56991 56991 11
[(CuL)2Pr(NO3)2]+ 97903 97902 21Pr(NO3)36H2O S6
[(CuL)Pr(NO3)2]+ 62196 62196 11
[(CuL)2Nd(NO3)2]+ 98001 98001 21Nd(NO3)36H2O S7
[(CuL)Nd(NO3)2]+ 62295 62294 11
[(CuL)2Sm(NO3)2]+ 99002 99002 21Sm(NO3)36H2O S8
[(CuL)Sm(NO3)2]+ 63296 63296 11
Table S4 Comparison of HOMO-LUMO gap with the overall electrochemical shift in 11 adducts
Complex Relative stabilization of HOMO-LUMO gap (max) with
respect to [CuL]+K+
(meV)
Expected shift with respect to [CuL]+K+
1198981198901198811 119890
= 119898119881
[E12 (ox) - E12 (red)] =E12 observed from
DPV (V)
Relative shift of E12 with respect to
[CuL]+K+
(mV)
[CuL]+K+ (943-943) = 0 0466-(-1487) =1953 1953-1953 = 0
[CuL]+Na+ (4868-943) = 3925 0487-(-1412) =1899 1953-1899 = 54
[CuL]+Li+ (19920-943) = 18977 0555-(-1207) = 1762 1953-1762 = 191
[CuL]+Ca2+ (25807-943) = 24864 0589-(-1111) = 1700 1953-1700 = 253
[CuL]+Mg2+ (28543-943) = 27600 0623-(-1107) = 1730 1953-1730 = 223
21
Table S5 Summary of UV-Vis and electrochemical properties of complexes 1 and 2
Complex 1 [CuL]+10 equiv
K+
Complex 2 [CuL]+10 equiv
Zn2+
max ( LMCT) nm 3655 362 344 nm 3325
E12 (ox) (V) from
DPV
0493 0898 0466 0913 0471 0612
0920
0652 0784
E12 (red) (V) from
DPV
-1175 (hump) -
1459
-1487 -0875 (hump)
-1011 -1477
Not done
10
Fig S15 Top UV-VIS spectra Middle CV (300 mVs-1 scan rate) and Bottom DPV (20 mVs-1 scan rate) of complex 1 at different potential range in presence of 100 equiv of TBAHFP in acetonitrile
11
Fig S16 Top UV-VIS spectra Middle CV (300 mVs-1 scan rate) and Bottom DPV (20 mVs-1 scan rate) of complex 2 at different potential range in presence of 100 equiv of TBAHFP in acetonitrile
12
Fig S17 Dependence of half-wave potentials (E12) of electrochemical reduction of the
heterometallic complexes ([(CuL)M]n+) vs pKa of M(aqua)n+ ions as measure of their Lewis
acidity
Fig S18 Electrochemical response of [CuL] in acetonitrile upon incremental addition of aquous
acetonirile (left) and the corresponding change in molar extinction coefficient of LMCT band
(right)
13
Fig S19 Electrochemical response of [CuL] + 10 eqv Zn2+ in acetonitrile upon incremental
addition of aquous acetonirile (left) and the corresponding change in molar extinction coefficient
of LMCT band (right)
Fig S20 Electrochemical response of [CuL] + 10 eqv Mg2+ in acetonitrile upon incremental
addition of aquous acetonirile (left) and the corresponding change in molar extinction coefficient
of LMCT band (right)
14
Fig S21 Correlation of shift of oxidation peak potential with equivalent of water added for
[CuL]+Mn+( Mn+ = Pr3+ Zn2+ Mg2+) (Solid line is guide for eye)
Fig S22 Correlation of change of molar absorptivity with equivalent of water added for
[CuL]+Mn+( Mn+ = Pr3+ Zn2+ Mg2+) (Solid line is guide for eye)
15
Fig S23 Correlation of the shift of oxidation peak potential with the change of molar extinction
coefficient of [CuL] in acetonitrile upon incremental addition of aquous acetonirile
Fig S24 Correlation of the shift of oxidation peak potential with the change of molar extinction
coefficient of [CuL]+10 eqv Zn2+ in acetonitrile upon incremental addition of aquous
acetonirile
16
Fig S25 Correlation of the shift of oxidation peak potential with the change of molar extinction
coefficient of [CuL]+10 eqv Mg2+ in acetonitrile upon incremental addition of aquous
acetonirile
Table S1 List of bond lengths (Aring) and bond angles (ordm) of complexes 1 and 2
M = K M = Zn
M(1)O(1) 2020(6) 2000(4)
M(1)O(2) 2179(5) 2279(5)
M(1)O(3) 2012(5) 1986(4)
M(1)O(4) 2184(6)) 2345(5)
M(1)O(5) 2058(6) 2062(5)
M(1)O(6) 2037(5) 2031(5)
Cu(1)O(1) 1920(5) 1909(5)
Cu(1)O(2) 1944(4) 1917(4)
Cu(1)N(1) 2004(6) 1982(6)
Cu(1)N(2) 1937(7) 1913(6)
Cu(2)O(3) 1909(5) 1922(5)
17
Cu(2)O(4) 1937(5) 1896(4)
Cu(2)N(3) 1966(5) 1963(5)
Cu(2)N(4) 1933(7) 1927(5)
O(1)M(1)O(2) 7448(18) 7182(17)
O(1)M(1)O(3) 1567(2) 14831(19)
O(1)M(1)O(4) 891(2) 8456(17)
O(1)M(1)O(5) 1020(2) 1061(2)
O(1)M(1)O(6) 942(2) 954(2)
O(2)M(1)O(3) 8738(19) 8400(18)
O(2)M(1)O(4) 813(2) 7719(17)
O(2)M(1)O(5) 929(2) 9441(18)
O(2)M(1)O(6) 1684(2) 16616(18)
O(3)M(1)O(4) 734(2) 7002(16)
O(3)M(1)O(5) 933(2) 9563(19)
O(3)M(1)O(6) 1028(2) 1058(2)
O(4)M(1)O(5) 1657(2) 16385(18)
O(4)M(1)O(6) 963(2) 9675(18)
O(5)M(1)O(6) 919(2) 943(2)
O(1)Cu(1)O(2) 824(2) 8238(18)
O(1)Cu(1)N(1) 905(2) 902(2)
O(1)Cu(1)N(2) 1693(3) 1690(2)
O(2)Cu(1)N(1) 1633(2) 1656(2)
O(2)Cu(1)N(2) 918(3) 920(2)
N(1)Cu(1)N(2) 974(3) 973(2)
O(2)Cu(2)O(3) 7047(16) 6993(16)
O(2)Cu(2)O(4) 684(2) 7092(17)
O(2)Cu(2)N(3) 982(2) 9683(17)
O(2)Cu(2)N(4) 1134(2) 11492(18)
18
O(3)Cu(2)O(4) 815(2) 8190(18)
O(3)Cu(2)N(3) 903(2) 901(2)
O(3)Cu(2)N(4) 1712(2) 1717(2)
O(4)Cu(2)N(3) 1660(3) 1671(2)
O(4)Cu(2)N(4) 925(3) 932(2)
N(3)Cu(2)N(4) 968(3) 959(2)
Table S2 Correlation of electrochemical response of previously reported 11 metallohost redox-inactive ion adducts derived from bicompartmental macrocyclic ligands containing adjacent N2O2 and 18-crown-6 like cavity with pKa of corresponding metal-aqua complex
[MnL](PF6)+MXn in acetonitrile MXn =
pKa E12 for Mn(IIIII) (V vs SCE)
KPF6 1625 0025LiClO4 1382 0055Ba(OTf)2 1336 0200Ca(OTf)2 1260 0245
Li+(expected)
[Li+(experimental) - Li+(expected)]
0176
0055 - 0176 =-0121
Data plotted from reference [16] of the main text
[NiL]+MXn in acetonitrileMXn =
pKa EPC for Ni(III)(V vs ferrocene)
NaPF6 1477 -165Ca(OTf)2 1260 -142Nd(OTf)3 843a -118Y(OTf)3 804a -122
Y3+(expected)
[Y3+(experimental) - Y3+(expected)]
-113
-122-(-113) =-009
aobtained from ref Data plotted from reference [17] of the main text
19
[56] of main text[CoL] + MXn in DMF MXn =
pKa E12 for Co(III)(V vs ferrocene)
K(OTf) 1625 -158Na(OTf) 1477 -158Ba(OTf)2 1336 -148Sr(OTf)2 1318 -144Ca(OTf)2 1260 -141
Na+(expected)
[Na+(experimental) - Na+(expected)]
-1515
-158 - (-1515)=-0065
Data plotted from reference [18] of the main text
[CuL]+Mn+ in DMSO Mn+=
pKa E12 for Cu(III)(V vs AgAgCl)
K+ 1625 -1277Na+ 1477 -1279Li+ 1382 -1286Ba2+ 1336 -1119Na+(expected)
[Na+(experimental) - Na+(expected)]
Li+(expected)
[Li+(experimental) - Li+(expected)]
-1185-1279-(-1185)=-0094
-1134-1286-(-1134)=-0152
Data plotted from reference [19] of the main text Line is guide for eye
[Mn(N)L] + MXn in acetonitrile MXn =
pKa E12 for Mn(VVI) (V vs ferrocene)
K(OTf) 1625 0616Na(OTf) 1477 0591Ba(OTf)2 1336 0805Sr(OTf)2 1318 0880
Na+(expected)
[Na+(experimental) - Na+(expected)]
0723
0591-0723 =-0132
Data plotted from reference [31] of the main text
20
Table S3 Masses of species obtained with their calculated values
[CuL]+ 10 eqv MXn
salts
Figure Species detected
with charge
Experimental
Mass (mz)
Calculated
Mass
(mz)
[CuL]M
[(CuL)2Li]+ 72116 72114 21Li(ClO4)3H2O S3
[(CuL)Li]+ 36407 36408 11
[(CuL)2Zn(ClO4)]+ 87701 87701 21
[(CuL)2Zn]2+ 39003 39003 21
Zn(ClO4)26H2O S4
[(CuL)Zn(ClO4)]+ 51994 51994 11
[(CuL)2Cd(ClO4)]+ 92698 92698 21
[(CuL)2Cd]2+ 41402 41401 21
Cd(ClO4)26H2O S5
[(CuL)Cd(ClO4)]+ 56991 56991 11
[(CuL)2Pr(NO3)2]+ 97903 97902 21Pr(NO3)36H2O S6
[(CuL)Pr(NO3)2]+ 62196 62196 11
[(CuL)2Nd(NO3)2]+ 98001 98001 21Nd(NO3)36H2O S7
[(CuL)Nd(NO3)2]+ 62295 62294 11
[(CuL)2Sm(NO3)2]+ 99002 99002 21Sm(NO3)36H2O S8
[(CuL)Sm(NO3)2]+ 63296 63296 11
Table S4 Comparison of HOMO-LUMO gap with the overall electrochemical shift in 11 adducts
Complex Relative stabilization of HOMO-LUMO gap (max) with
respect to [CuL]+K+
(meV)
Expected shift with respect to [CuL]+K+
1198981198901198811 119890
= 119898119881
[E12 (ox) - E12 (red)] =E12 observed from
DPV (V)
Relative shift of E12 with respect to
[CuL]+K+
(mV)
[CuL]+K+ (943-943) = 0 0466-(-1487) =1953 1953-1953 = 0
[CuL]+Na+ (4868-943) = 3925 0487-(-1412) =1899 1953-1899 = 54
[CuL]+Li+ (19920-943) = 18977 0555-(-1207) = 1762 1953-1762 = 191
[CuL]+Ca2+ (25807-943) = 24864 0589-(-1111) = 1700 1953-1700 = 253
[CuL]+Mg2+ (28543-943) = 27600 0623-(-1107) = 1730 1953-1730 = 223
21
Table S5 Summary of UV-Vis and electrochemical properties of complexes 1 and 2
Complex 1 [CuL]+10 equiv
K+
Complex 2 [CuL]+10 equiv
Zn2+
max ( LMCT) nm 3655 362 344 nm 3325
E12 (ox) (V) from
DPV
0493 0898 0466 0913 0471 0612
0920
0652 0784
E12 (red) (V) from
DPV
-1175 (hump) -
1459
-1487 -0875 (hump)
-1011 -1477
Not done
11
Fig S16 Top UV-VIS spectra Middle CV (300 mVs-1 scan rate) and Bottom DPV (20 mVs-1 scan rate) of complex 2 at different potential range in presence of 100 equiv of TBAHFP in acetonitrile
12
Fig S17 Dependence of half-wave potentials (E12) of electrochemical reduction of the
heterometallic complexes ([(CuL)M]n+) vs pKa of M(aqua)n+ ions as measure of their Lewis
acidity
Fig S18 Electrochemical response of [CuL] in acetonitrile upon incremental addition of aquous
acetonirile (left) and the corresponding change in molar extinction coefficient of LMCT band
(right)
13
Fig S19 Electrochemical response of [CuL] + 10 eqv Zn2+ in acetonitrile upon incremental
addition of aquous acetonirile (left) and the corresponding change in molar extinction coefficient
of LMCT band (right)
Fig S20 Electrochemical response of [CuL] + 10 eqv Mg2+ in acetonitrile upon incremental
addition of aquous acetonirile (left) and the corresponding change in molar extinction coefficient
of LMCT band (right)
14
Fig S21 Correlation of shift of oxidation peak potential with equivalent of water added for
[CuL]+Mn+( Mn+ = Pr3+ Zn2+ Mg2+) (Solid line is guide for eye)
Fig S22 Correlation of change of molar absorptivity with equivalent of water added for
[CuL]+Mn+( Mn+ = Pr3+ Zn2+ Mg2+) (Solid line is guide for eye)
15
Fig S23 Correlation of the shift of oxidation peak potential with the change of molar extinction
coefficient of [CuL] in acetonitrile upon incremental addition of aquous acetonirile
Fig S24 Correlation of the shift of oxidation peak potential with the change of molar extinction
coefficient of [CuL]+10 eqv Zn2+ in acetonitrile upon incremental addition of aquous
acetonirile
16
Fig S25 Correlation of the shift of oxidation peak potential with the change of molar extinction
coefficient of [CuL]+10 eqv Mg2+ in acetonitrile upon incremental addition of aquous
acetonirile
Table S1 List of bond lengths (Aring) and bond angles (ordm) of complexes 1 and 2
M = K M = Zn
M(1)O(1) 2020(6) 2000(4)
M(1)O(2) 2179(5) 2279(5)
M(1)O(3) 2012(5) 1986(4)
M(1)O(4) 2184(6)) 2345(5)
M(1)O(5) 2058(6) 2062(5)
M(1)O(6) 2037(5) 2031(5)
Cu(1)O(1) 1920(5) 1909(5)
Cu(1)O(2) 1944(4) 1917(4)
Cu(1)N(1) 2004(6) 1982(6)
Cu(1)N(2) 1937(7) 1913(6)
Cu(2)O(3) 1909(5) 1922(5)
17
Cu(2)O(4) 1937(5) 1896(4)
Cu(2)N(3) 1966(5) 1963(5)
Cu(2)N(4) 1933(7) 1927(5)
O(1)M(1)O(2) 7448(18) 7182(17)
O(1)M(1)O(3) 1567(2) 14831(19)
O(1)M(1)O(4) 891(2) 8456(17)
O(1)M(1)O(5) 1020(2) 1061(2)
O(1)M(1)O(6) 942(2) 954(2)
O(2)M(1)O(3) 8738(19) 8400(18)
O(2)M(1)O(4) 813(2) 7719(17)
O(2)M(1)O(5) 929(2) 9441(18)
O(2)M(1)O(6) 1684(2) 16616(18)
O(3)M(1)O(4) 734(2) 7002(16)
O(3)M(1)O(5) 933(2) 9563(19)
O(3)M(1)O(6) 1028(2) 1058(2)
O(4)M(1)O(5) 1657(2) 16385(18)
O(4)M(1)O(6) 963(2) 9675(18)
O(5)M(1)O(6) 919(2) 943(2)
O(1)Cu(1)O(2) 824(2) 8238(18)
O(1)Cu(1)N(1) 905(2) 902(2)
O(1)Cu(1)N(2) 1693(3) 1690(2)
O(2)Cu(1)N(1) 1633(2) 1656(2)
O(2)Cu(1)N(2) 918(3) 920(2)
N(1)Cu(1)N(2) 974(3) 973(2)
O(2)Cu(2)O(3) 7047(16) 6993(16)
O(2)Cu(2)O(4) 684(2) 7092(17)
O(2)Cu(2)N(3) 982(2) 9683(17)
O(2)Cu(2)N(4) 1134(2) 11492(18)
18
O(3)Cu(2)O(4) 815(2) 8190(18)
O(3)Cu(2)N(3) 903(2) 901(2)
O(3)Cu(2)N(4) 1712(2) 1717(2)
O(4)Cu(2)N(3) 1660(3) 1671(2)
O(4)Cu(2)N(4) 925(3) 932(2)
N(3)Cu(2)N(4) 968(3) 959(2)
Table S2 Correlation of electrochemical response of previously reported 11 metallohost redox-inactive ion adducts derived from bicompartmental macrocyclic ligands containing adjacent N2O2 and 18-crown-6 like cavity with pKa of corresponding metal-aqua complex
[MnL](PF6)+MXn in acetonitrile MXn =
pKa E12 for Mn(IIIII) (V vs SCE)
KPF6 1625 0025LiClO4 1382 0055Ba(OTf)2 1336 0200Ca(OTf)2 1260 0245
Li+(expected)
[Li+(experimental) - Li+(expected)]
0176
0055 - 0176 =-0121
Data plotted from reference [16] of the main text
[NiL]+MXn in acetonitrileMXn =
pKa EPC for Ni(III)(V vs ferrocene)
NaPF6 1477 -165Ca(OTf)2 1260 -142Nd(OTf)3 843a -118Y(OTf)3 804a -122
Y3+(expected)
[Y3+(experimental) - Y3+(expected)]
-113
-122-(-113) =-009
aobtained from ref Data plotted from reference [17] of the main text
19
[56] of main text[CoL] + MXn in DMF MXn =
pKa E12 for Co(III)(V vs ferrocene)
K(OTf) 1625 -158Na(OTf) 1477 -158Ba(OTf)2 1336 -148Sr(OTf)2 1318 -144Ca(OTf)2 1260 -141
Na+(expected)
[Na+(experimental) - Na+(expected)]
-1515
-158 - (-1515)=-0065
Data plotted from reference [18] of the main text
[CuL]+Mn+ in DMSO Mn+=
pKa E12 for Cu(III)(V vs AgAgCl)
K+ 1625 -1277Na+ 1477 -1279Li+ 1382 -1286Ba2+ 1336 -1119Na+(expected)
[Na+(experimental) - Na+(expected)]
Li+(expected)
[Li+(experimental) - Li+(expected)]
-1185-1279-(-1185)=-0094
-1134-1286-(-1134)=-0152
Data plotted from reference [19] of the main text Line is guide for eye
[Mn(N)L] + MXn in acetonitrile MXn =
pKa E12 for Mn(VVI) (V vs ferrocene)
K(OTf) 1625 0616Na(OTf) 1477 0591Ba(OTf)2 1336 0805Sr(OTf)2 1318 0880
Na+(expected)
[Na+(experimental) - Na+(expected)]
0723
0591-0723 =-0132
Data plotted from reference [31] of the main text
20
Table S3 Masses of species obtained with their calculated values
[CuL]+ 10 eqv MXn
salts
Figure Species detected
with charge
Experimental
Mass (mz)
Calculated
Mass
(mz)
[CuL]M
[(CuL)2Li]+ 72116 72114 21Li(ClO4)3H2O S3
[(CuL)Li]+ 36407 36408 11
[(CuL)2Zn(ClO4)]+ 87701 87701 21
[(CuL)2Zn]2+ 39003 39003 21
Zn(ClO4)26H2O S4
[(CuL)Zn(ClO4)]+ 51994 51994 11
[(CuL)2Cd(ClO4)]+ 92698 92698 21
[(CuL)2Cd]2+ 41402 41401 21
Cd(ClO4)26H2O S5
[(CuL)Cd(ClO4)]+ 56991 56991 11
[(CuL)2Pr(NO3)2]+ 97903 97902 21Pr(NO3)36H2O S6
[(CuL)Pr(NO3)2]+ 62196 62196 11
[(CuL)2Nd(NO3)2]+ 98001 98001 21Nd(NO3)36H2O S7
[(CuL)Nd(NO3)2]+ 62295 62294 11
[(CuL)2Sm(NO3)2]+ 99002 99002 21Sm(NO3)36H2O S8
[(CuL)Sm(NO3)2]+ 63296 63296 11
Table S4 Comparison of HOMO-LUMO gap with the overall electrochemical shift in 11 adducts
Complex Relative stabilization of HOMO-LUMO gap (max) with
respect to [CuL]+K+
(meV)
Expected shift with respect to [CuL]+K+
1198981198901198811 119890
= 119898119881
[E12 (ox) - E12 (red)] =E12 observed from
DPV (V)
Relative shift of E12 with respect to
[CuL]+K+
(mV)
[CuL]+K+ (943-943) = 0 0466-(-1487) =1953 1953-1953 = 0
[CuL]+Na+ (4868-943) = 3925 0487-(-1412) =1899 1953-1899 = 54
[CuL]+Li+ (19920-943) = 18977 0555-(-1207) = 1762 1953-1762 = 191
[CuL]+Ca2+ (25807-943) = 24864 0589-(-1111) = 1700 1953-1700 = 253
[CuL]+Mg2+ (28543-943) = 27600 0623-(-1107) = 1730 1953-1730 = 223
21
Table S5 Summary of UV-Vis and electrochemical properties of complexes 1 and 2
Complex 1 [CuL]+10 equiv
K+
Complex 2 [CuL]+10 equiv
Zn2+
max ( LMCT) nm 3655 362 344 nm 3325
E12 (ox) (V) from
DPV
0493 0898 0466 0913 0471 0612
0920
0652 0784
E12 (red) (V) from
DPV
-1175 (hump) -
1459
-1487 -0875 (hump)
-1011 -1477
Not done
12
Fig S17 Dependence of half-wave potentials (E12) of electrochemical reduction of the
heterometallic complexes ([(CuL)M]n+) vs pKa of M(aqua)n+ ions as measure of their Lewis
acidity
Fig S18 Electrochemical response of [CuL] in acetonitrile upon incremental addition of aquous
acetonirile (left) and the corresponding change in molar extinction coefficient of LMCT band
(right)
13
Fig S19 Electrochemical response of [CuL] + 10 eqv Zn2+ in acetonitrile upon incremental
addition of aquous acetonirile (left) and the corresponding change in molar extinction coefficient
of LMCT band (right)
Fig S20 Electrochemical response of [CuL] + 10 eqv Mg2+ in acetonitrile upon incremental
addition of aquous acetonirile (left) and the corresponding change in molar extinction coefficient
of LMCT band (right)
14
Fig S21 Correlation of shift of oxidation peak potential with equivalent of water added for
[CuL]+Mn+( Mn+ = Pr3+ Zn2+ Mg2+) (Solid line is guide for eye)
Fig S22 Correlation of change of molar absorptivity with equivalent of water added for
[CuL]+Mn+( Mn+ = Pr3+ Zn2+ Mg2+) (Solid line is guide for eye)
15
Fig S23 Correlation of the shift of oxidation peak potential with the change of molar extinction
coefficient of [CuL] in acetonitrile upon incremental addition of aquous acetonirile
Fig S24 Correlation of the shift of oxidation peak potential with the change of molar extinction
coefficient of [CuL]+10 eqv Zn2+ in acetonitrile upon incremental addition of aquous
acetonirile
16
Fig S25 Correlation of the shift of oxidation peak potential with the change of molar extinction
coefficient of [CuL]+10 eqv Mg2+ in acetonitrile upon incremental addition of aquous
acetonirile
Table S1 List of bond lengths (Aring) and bond angles (ordm) of complexes 1 and 2
M = K M = Zn
M(1)O(1) 2020(6) 2000(4)
M(1)O(2) 2179(5) 2279(5)
M(1)O(3) 2012(5) 1986(4)
M(1)O(4) 2184(6)) 2345(5)
M(1)O(5) 2058(6) 2062(5)
M(1)O(6) 2037(5) 2031(5)
Cu(1)O(1) 1920(5) 1909(5)
Cu(1)O(2) 1944(4) 1917(4)
Cu(1)N(1) 2004(6) 1982(6)
Cu(1)N(2) 1937(7) 1913(6)
Cu(2)O(3) 1909(5) 1922(5)
17
Cu(2)O(4) 1937(5) 1896(4)
Cu(2)N(3) 1966(5) 1963(5)
Cu(2)N(4) 1933(7) 1927(5)
O(1)M(1)O(2) 7448(18) 7182(17)
O(1)M(1)O(3) 1567(2) 14831(19)
O(1)M(1)O(4) 891(2) 8456(17)
O(1)M(1)O(5) 1020(2) 1061(2)
O(1)M(1)O(6) 942(2) 954(2)
O(2)M(1)O(3) 8738(19) 8400(18)
O(2)M(1)O(4) 813(2) 7719(17)
O(2)M(1)O(5) 929(2) 9441(18)
O(2)M(1)O(6) 1684(2) 16616(18)
O(3)M(1)O(4) 734(2) 7002(16)
O(3)M(1)O(5) 933(2) 9563(19)
O(3)M(1)O(6) 1028(2) 1058(2)
O(4)M(1)O(5) 1657(2) 16385(18)
O(4)M(1)O(6) 963(2) 9675(18)
O(5)M(1)O(6) 919(2) 943(2)
O(1)Cu(1)O(2) 824(2) 8238(18)
O(1)Cu(1)N(1) 905(2) 902(2)
O(1)Cu(1)N(2) 1693(3) 1690(2)
O(2)Cu(1)N(1) 1633(2) 1656(2)
O(2)Cu(1)N(2) 918(3) 920(2)
N(1)Cu(1)N(2) 974(3) 973(2)
O(2)Cu(2)O(3) 7047(16) 6993(16)
O(2)Cu(2)O(4) 684(2) 7092(17)
O(2)Cu(2)N(3) 982(2) 9683(17)
O(2)Cu(2)N(4) 1134(2) 11492(18)
18
O(3)Cu(2)O(4) 815(2) 8190(18)
O(3)Cu(2)N(3) 903(2) 901(2)
O(3)Cu(2)N(4) 1712(2) 1717(2)
O(4)Cu(2)N(3) 1660(3) 1671(2)
O(4)Cu(2)N(4) 925(3) 932(2)
N(3)Cu(2)N(4) 968(3) 959(2)
Table S2 Correlation of electrochemical response of previously reported 11 metallohost redox-inactive ion adducts derived from bicompartmental macrocyclic ligands containing adjacent N2O2 and 18-crown-6 like cavity with pKa of corresponding metal-aqua complex
[MnL](PF6)+MXn in acetonitrile MXn =
pKa E12 for Mn(IIIII) (V vs SCE)
KPF6 1625 0025LiClO4 1382 0055Ba(OTf)2 1336 0200Ca(OTf)2 1260 0245
Li+(expected)
[Li+(experimental) - Li+(expected)]
0176
0055 - 0176 =-0121
Data plotted from reference [16] of the main text
[NiL]+MXn in acetonitrileMXn =
pKa EPC for Ni(III)(V vs ferrocene)
NaPF6 1477 -165Ca(OTf)2 1260 -142Nd(OTf)3 843a -118Y(OTf)3 804a -122
Y3+(expected)
[Y3+(experimental) - Y3+(expected)]
-113
-122-(-113) =-009
aobtained from ref Data plotted from reference [17] of the main text
19
[56] of main text[CoL] + MXn in DMF MXn =
pKa E12 for Co(III)(V vs ferrocene)
K(OTf) 1625 -158Na(OTf) 1477 -158Ba(OTf)2 1336 -148Sr(OTf)2 1318 -144Ca(OTf)2 1260 -141
Na+(expected)
[Na+(experimental) - Na+(expected)]
-1515
-158 - (-1515)=-0065
Data plotted from reference [18] of the main text
[CuL]+Mn+ in DMSO Mn+=
pKa E12 for Cu(III)(V vs AgAgCl)
K+ 1625 -1277Na+ 1477 -1279Li+ 1382 -1286Ba2+ 1336 -1119Na+(expected)
[Na+(experimental) - Na+(expected)]
Li+(expected)
[Li+(experimental) - Li+(expected)]
-1185-1279-(-1185)=-0094
-1134-1286-(-1134)=-0152
Data plotted from reference [19] of the main text Line is guide for eye
[Mn(N)L] + MXn in acetonitrile MXn =
pKa E12 for Mn(VVI) (V vs ferrocene)
K(OTf) 1625 0616Na(OTf) 1477 0591Ba(OTf)2 1336 0805Sr(OTf)2 1318 0880
Na+(expected)
[Na+(experimental) - Na+(expected)]
0723
0591-0723 =-0132
Data plotted from reference [31] of the main text
20
Table S3 Masses of species obtained with their calculated values
[CuL]+ 10 eqv MXn
salts
Figure Species detected
with charge
Experimental
Mass (mz)
Calculated
Mass
(mz)
[CuL]M
[(CuL)2Li]+ 72116 72114 21Li(ClO4)3H2O S3
[(CuL)Li]+ 36407 36408 11
[(CuL)2Zn(ClO4)]+ 87701 87701 21
[(CuL)2Zn]2+ 39003 39003 21
Zn(ClO4)26H2O S4
[(CuL)Zn(ClO4)]+ 51994 51994 11
[(CuL)2Cd(ClO4)]+ 92698 92698 21
[(CuL)2Cd]2+ 41402 41401 21
Cd(ClO4)26H2O S5
[(CuL)Cd(ClO4)]+ 56991 56991 11
[(CuL)2Pr(NO3)2]+ 97903 97902 21Pr(NO3)36H2O S6
[(CuL)Pr(NO3)2]+ 62196 62196 11
[(CuL)2Nd(NO3)2]+ 98001 98001 21Nd(NO3)36H2O S7
[(CuL)Nd(NO3)2]+ 62295 62294 11
[(CuL)2Sm(NO3)2]+ 99002 99002 21Sm(NO3)36H2O S8
[(CuL)Sm(NO3)2]+ 63296 63296 11
Table S4 Comparison of HOMO-LUMO gap with the overall electrochemical shift in 11 adducts
Complex Relative stabilization of HOMO-LUMO gap (max) with
respect to [CuL]+K+
(meV)
Expected shift with respect to [CuL]+K+
1198981198901198811 119890
= 119898119881
[E12 (ox) - E12 (red)] =E12 observed from
DPV (V)
Relative shift of E12 with respect to
[CuL]+K+
(mV)
[CuL]+K+ (943-943) = 0 0466-(-1487) =1953 1953-1953 = 0
[CuL]+Na+ (4868-943) = 3925 0487-(-1412) =1899 1953-1899 = 54
[CuL]+Li+ (19920-943) = 18977 0555-(-1207) = 1762 1953-1762 = 191
[CuL]+Ca2+ (25807-943) = 24864 0589-(-1111) = 1700 1953-1700 = 253
[CuL]+Mg2+ (28543-943) = 27600 0623-(-1107) = 1730 1953-1730 = 223
21
Table S5 Summary of UV-Vis and electrochemical properties of complexes 1 and 2
Complex 1 [CuL]+10 equiv
K+
Complex 2 [CuL]+10 equiv
Zn2+
max ( LMCT) nm 3655 362 344 nm 3325
E12 (ox) (V) from
DPV
0493 0898 0466 0913 0471 0612
0920
0652 0784
E12 (red) (V) from
DPV
-1175 (hump) -
1459
-1487 -0875 (hump)
-1011 -1477
Not done
13
Fig S19 Electrochemical response of [CuL] + 10 eqv Zn2+ in acetonitrile upon incremental
addition of aquous acetonirile (left) and the corresponding change in molar extinction coefficient
of LMCT band (right)
Fig S20 Electrochemical response of [CuL] + 10 eqv Mg2+ in acetonitrile upon incremental
addition of aquous acetonirile (left) and the corresponding change in molar extinction coefficient
of LMCT band (right)
14
Fig S21 Correlation of shift of oxidation peak potential with equivalent of water added for
[CuL]+Mn+( Mn+ = Pr3+ Zn2+ Mg2+) (Solid line is guide for eye)
Fig S22 Correlation of change of molar absorptivity with equivalent of water added for
[CuL]+Mn+( Mn+ = Pr3+ Zn2+ Mg2+) (Solid line is guide for eye)
15
Fig S23 Correlation of the shift of oxidation peak potential with the change of molar extinction
coefficient of [CuL] in acetonitrile upon incremental addition of aquous acetonirile
Fig S24 Correlation of the shift of oxidation peak potential with the change of molar extinction
coefficient of [CuL]+10 eqv Zn2+ in acetonitrile upon incremental addition of aquous
acetonirile
16
Fig S25 Correlation of the shift of oxidation peak potential with the change of molar extinction
coefficient of [CuL]+10 eqv Mg2+ in acetonitrile upon incremental addition of aquous
acetonirile
Table S1 List of bond lengths (Aring) and bond angles (ordm) of complexes 1 and 2
M = K M = Zn
M(1)O(1) 2020(6) 2000(4)
M(1)O(2) 2179(5) 2279(5)
M(1)O(3) 2012(5) 1986(4)
M(1)O(4) 2184(6)) 2345(5)
M(1)O(5) 2058(6) 2062(5)
M(1)O(6) 2037(5) 2031(5)
Cu(1)O(1) 1920(5) 1909(5)
Cu(1)O(2) 1944(4) 1917(4)
Cu(1)N(1) 2004(6) 1982(6)
Cu(1)N(2) 1937(7) 1913(6)
Cu(2)O(3) 1909(5) 1922(5)
17
Cu(2)O(4) 1937(5) 1896(4)
Cu(2)N(3) 1966(5) 1963(5)
Cu(2)N(4) 1933(7) 1927(5)
O(1)M(1)O(2) 7448(18) 7182(17)
O(1)M(1)O(3) 1567(2) 14831(19)
O(1)M(1)O(4) 891(2) 8456(17)
O(1)M(1)O(5) 1020(2) 1061(2)
O(1)M(1)O(6) 942(2) 954(2)
O(2)M(1)O(3) 8738(19) 8400(18)
O(2)M(1)O(4) 813(2) 7719(17)
O(2)M(1)O(5) 929(2) 9441(18)
O(2)M(1)O(6) 1684(2) 16616(18)
O(3)M(1)O(4) 734(2) 7002(16)
O(3)M(1)O(5) 933(2) 9563(19)
O(3)M(1)O(6) 1028(2) 1058(2)
O(4)M(1)O(5) 1657(2) 16385(18)
O(4)M(1)O(6) 963(2) 9675(18)
O(5)M(1)O(6) 919(2) 943(2)
O(1)Cu(1)O(2) 824(2) 8238(18)
O(1)Cu(1)N(1) 905(2) 902(2)
O(1)Cu(1)N(2) 1693(3) 1690(2)
O(2)Cu(1)N(1) 1633(2) 1656(2)
O(2)Cu(1)N(2) 918(3) 920(2)
N(1)Cu(1)N(2) 974(3) 973(2)
O(2)Cu(2)O(3) 7047(16) 6993(16)
O(2)Cu(2)O(4) 684(2) 7092(17)
O(2)Cu(2)N(3) 982(2) 9683(17)
O(2)Cu(2)N(4) 1134(2) 11492(18)
18
O(3)Cu(2)O(4) 815(2) 8190(18)
O(3)Cu(2)N(3) 903(2) 901(2)
O(3)Cu(2)N(4) 1712(2) 1717(2)
O(4)Cu(2)N(3) 1660(3) 1671(2)
O(4)Cu(2)N(4) 925(3) 932(2)
N(3)Cu(2)N(4) 968(3) 959(2)
Table S2 Correlation of electrochemical response of previously reported 11 metallohost redox-inactive ion adducts derived from bicompartmental macrocyclic ligands containing adjacent N2O2 and 18-crown-6 like cavity with pKa of corresponding metal-aqua complex
[MnL](PF6)+MXn in acetonitrile MXn =
pKa E12 for Mn(IIIII) (V vs SCE)
KPF6 1625 0025LiClO4 1382 0055Ba(OTf)2 1336 0200Ca(OTf)2 1260 0245
Li+(expected)
[Li+(experimental) - Li+(expected)]
0176
0055 - 0176 =-0121
Data plotted from reference [16] of the main text
[NiL]+MXn in acetonitrileMXn =
pKa EPC for Ni(III)(V vs ferrocene)
NaPF6 1477 -165Ca(OTf)2 1260 -142Nd(OTf)3 843a -118Y(OTf)3 804a -122
Y3+(expected)
[Y3+(experimental) - Y3+(expected)]
-113
-122-(-113) =-009
aobtained from ref Data plotted from reference [17] of the main text
19
[56] of main text[CoL] + MXn in DMF MXn =
pKa E12 for Co(III)(V vs ferrocene)
K(OTf) 1625 -158Na(OTf) 1477 -158Ba(OTf)2 1336 -148Sr(OTf)2 1318 -144Ca(OTf)2 1260 -141
Na+(expected)
[Na+(experimental) - Na+(expected)]
-1515
-158 - (-1515)=-0065
Data plotted from reference [18] of the main text
[CuL]+Mn+ in DMSO Mn+=
pKa E12 for Cu(III)(V vs AgAgCl)
K+ 1625 -1277Na+ 1477 -1279Li+ 1382 -1286Ba2+ 1336 -1119Na+(expected)
[Na+(experimental) - Na+(expected)]
Li+(expected)
[Li+(experimental) - Li+(expected)]
-1185-1279-(-1185)=-0094
-1134-1286-(-1134)=-0152
Data plotted from reference [19] of the main text Line is guide for eye
[Mn(N)L] + MXn in acetonitrile MXn =
pKa E12 for Mn(VVI) (V vs ferrocene)
K(OTf) 1625 0616Na(OTf) 1477 0591Ba(OTf)2 1336 0805Sr(OTf)2 1318 0880
Na+(expected)
[Na+(experimental) - Na+(expected)]
0723
0591-0723 =-0132
Data plotted from reference [31] of the main text
20
Table S3 Masses of species obtained with their calculated values
[CuL]+ 10 eqv MXn
salts
Figure Species detected
with charge
Experimental
Mass (mz)
Calculated
Mass
(mz)
[CuL]M
[(CuL)2Li]+ 72116 72114 21Li(ClO4)3H2O S3
[(CuL)Li]+ 36407 36408 11
[(CuL)2Zn(ClO4)]+ 87701 87701 21
[(CuL)2Zn]2+ 39003 39003 21
Zn(ClO4)26H2O S4
[(CuL)Zn(ClO4)]+ 51994 51994 11
[(CuL)2Cd(ClO4)]+ 92698 92698 21
[(CuL)2Cd]2+ 41402 41401 21
Cd(ClO4)26H2O S5
[(CuL)Cd(ClO4)]+ 56991 56991 11
[(CuL)2Pr(NO3)2]+ 97903 97902 21Pr(NO3)36H2O S6
[(CuL)Pr(NO3)2]+ 62196 62196 11
[(CuL)2Nd(NO3)2]+ 98001 98001 21Nd(NO3)36H2O S7
[(CuL)Nd(NO3)2]+ 62295 62294 11
[(CuL)2Sm(NO3)2]+ 99002 99002 21Sm(NO3)36H2O S8
[(CuL)Sm(NO3)2]+ 63296 63296 11
Table S4 Comparison of HOMO-LUMO gap with the overall electrochemical shift in 11 adducts
Complex Relative stabilization of HOMO-LUMO gap (max) with
respect to [CuL]+K+
(meV)
Expected shift with respect to [CuL]+K+
1198981198901198811 119890
= 119898119881
[E12 (ox) - E12 (red)] =E12 observed from
DPV (V)
Relative shift of E12 with respect to
[CuL]+K+
(mV)
[CuL]+K+ (943-943) = 0 0466-(-1487) =1953 1953-1953 = 0
[CuL]+Na+ (4868-943) = 3925 0487-(-1412) =1899 1953-1899 = 54
[CuL]+Li+ (19920-943) = 18977 0555-(-1207) = 1762 1953-1762 = 191
[CuL]+Ca2+ (25807-943) = 24864 0589-(-1111) = 1700 1953-1700 = 253
[CuL]+Mg2+ (28543-943) = 27600 0623-(-1107) = 1730 1953-1730 = 223
21
Table S5 Summary of UV-Vis and electrochemical properties of complexes 1 and 2
Complex 1 [CuL]+10 equiv
K+
Complex 2 [CuL]+10 equiv
Zn2+
max ( LMCT) nm 3655 362 344 nm 3325
E12 (ox) (V) from
DPV
0493 0898 0466 0913 0471 0612
0920
0652 0784
E12 (red) (V) from
DPV
-1175 (hump) -
1459
-1487 -0875 (hump)
-1011 -1477
Not done
14
Fig S21 Correlation of shift of oxidation peak potential with equivalent of water added for
[CuL]+Mn+( Mn+ = Pr3+ Zn2+ Mg2+) (Solid line is guide for eye)
Fig S22 Correlation of change of molar absorptivity with equivalent of water added for
[CuL]+Mn+( Mn+ = Pr3+ Zn2+ Mg2+) (Solid line is guide for eye)
15
Fig S23 Correlation of the shift of oxidation peak potential with the change of molar extinction
coefficient of [CuL] in acetonitrile upon incremental addition of aquous acetonirile
Fig S24 Correlation of the shift of oxidation peak potential with the change of molar extinction
coefficient of [CuL]+10 eqv Zn2+ in acetonitrile upon incremental addition of aquous
acetonirile
16
Fig S25 Correlation of the shift of oxidation peak potential with the change of molar extinction
coefficient of [CuL]+10 eqv Mg2+ in acetonitrile upon incremental addition of aquous
acetonirile
Table S1 List of bond lengths (Aring) and bond angles (ordm) of complexes 1 and 2
M = K M = Zn
M(1)O(1) 2020(6) 2000(4)
M(1)O(2) 2179(5) 2279(5)
M(1)O(3) 2012(5) 1986(4)
M(1)O(4) 2184(6)) 2345(5)
M(1)O(5) 2058(6) 2062(5)
M(1)O(6) 2037(5) 2031(5)
Cu(1)O(1) 1920(5) 1909(5)
Cu(1)O(2) 1944(4) 1917(4)
Cu(1)N(1) 2004(6) 1982(6)
Cu(1)N(2) 1937(7) 1913(6)
Cu(2)O(3) 1909(5) 1922(5)
17
Cu(2)O(4) 1937(5) 1896(4)
Cu(2)N(3) 1966(5) 1963(5)
Cu(2)N(4) 1933(7) 1927(5)
O(1)M(1)O(2) 7448(18) 7182(17)
O(1)M(1)O(3) 1567(2) 14831(19)
O(1)M(1)O(4) 891(2) 8456(17)
O(1)M(1)O(5) 1020(2) 1061(2)
O(1)M(1)O(6) 942(2) 954(2)
O(2)M(1)O(3) 8738(19) 8400(18)
O(2)M(1)O(4) 813(2) 7719(17)
O(2)M(1)O(5) 929(2) 9441(18)
O(2)M(1)O(6) 1684(2) 16616(18)
O(3)M(1)O(4) 734(2) 7002(16)
O(3)M(1)O(5) 933(2) 9563(19)
O(3)M(1)O(6) 1028(2) 1058(2)
O(4)M(1)O(5) 1657(2) 16385(18)
O(4)M(1)O(6) 963(2) 9675(18)
O(5)M(1)O(6) 919(2) 943(2)
O(1)Cu(1)O(2) 824(2) 8238(18)
O(1)Cu(1)N(1) 905(2) 902(2)
O(1)Cu(1)N(2) 1693(3) 1690(2)
O(2)Cu(1)N(1) 1633(2) 1656(2)
O(2)Cu(1)N(2) 918(3) 920(2)
N(1)Cu(1)N(2) 974(3) 973(2)
O(2)Cu(2)O(3) 7047(16) 6993(16)
O(2)Cu(2)O(4) 684(2) 7092(17)
O(2)Cu(2)N(3) 982(2) 9683(17)
O(2)Cu(2)N(4) 1134(2) 11492(18)
18
O(3)Cu(2)O(4) 815(2) 8190(18)
O(3)Cu(2)N(3) 903(2) 901(2)
O(3)Cu(2)N(4) 1712(2) 1717(2)
O(4)Cu(2)N(3) 1660(3) 1671(2)
O(4)Cu(2)N(4) 925(3) 932(2)
N(3)Cu(2)N(4) 968(3) 959(2)
Table S2 Correlation of electrochemical response of previously reported 11 metallohost redox-inactive ion adducts derived from bicompartmental macrocyclic ligands containing adjacent N2O2 and 18-crown-6 like cavity with pKa of corresponding metal-aqua complex
[MnL](PF6)+MXn in acetonitrile MXn =
pKa E12 for Mn(IIIII) (V vs SCE)
KPF6 1625 0025LiClO4 1382 0055Ba(OTf)2 1336 0200Ca(OTf)2 1260 0245
Li+(expected)
[Li+(experimental) - Li+(expected)]
0176
0055 - 0176 =-0121
Data plotted from reference [16] of the main text
[NiL]+MXn in acetonitrileMXn =
pKa EPC for Ni(III)(V vs ferrocene)
NaPF6 1477 -165Ca(OTf)2 1260 -142Nd(OTf)3 843a -118Y(OTf)3 804a -122
Y3+(expected)
[Y3+(experimental) - Y3+(expected)]
-113
-122-(-113) =-009
aobtained from ref Data plotted from reference [17] of the main text
19
[56] of main text[CoL] + MXn in DMF MXn =
pKa E12 for Co(III)(V vs ferrocene)
K(OTf) 1625 -158Na(OTf) 1477 -158Ba(OTf)2 1336 -148Sr(OTf)2 1318 -144Ca(OTf)2 1260 -141
Na+(expected)
[Na+(experimental) - Na+(expected)]
-1515
-158 - (-1515)=-0065
Data plotted from reference [18] of the main text
[CuL]+Mn+ in DMSO Mn+=
pKa E12 for Cu(III)(V vs AgAgCl)
K+ 1625 -1277Na+ 1477 -1279Li+ 1382 -1286Ba2+ 1336 -1119Na+(expected)
[Na+(experimental) - Na+(expected)]
Li+(expected)
[Li+(experimental) - Li+(expected)]
-1185-1279-(-1185)=-0094
-1134-1286-(-1134)=-0152
Data plotted from reference [19] of the main text Line is guide for eye
[Mn(N)L] + MXn in acetonitrile MXn =
pKa E12 for Mn(VVI) (V vs ferrocene)
K(OTf) 1625 0616Na(OTf) 1477 0591Ba(OTf)2 1336 0805Sr(OTf)2 1318 0880
Na+(expected)
[Na+(experimental) - Na+(expected)]
0723
0591-0723 =-0132
Data plotted from reference [31] of the main text
20
Table S3 Masses of species obtained with their calculated values
[CuL]+ 10 eqv MXn
salts
Figure Species detected
with charge
Experimental
Mass (mz)
Calculated
Mass
(mz)
[CuL]M
[(CuL)2Li]+ 72116 72114 21Li(ClO4)3H2O S3
[(CuL)Li]+ 36407 36408 11
[(CuL)2Zn(ClO4)]+ 87701 87701 21
[(CuL)2Zn]2+ 39003 39003 21
Zn(ClO4)26H2O S4
[(CuL)Zn(ClO4)]+ 51994 51994 11
[(CuL)2Cd(ClO4)]+ 92698 92698 21
[(CuL)2Cd]2+ 41402 41401 21
Cd(ClO4)26H2O S5
[(CuL)Cd(ClO4)]+ 56991 56991 11
[(CuL)2Pr(NO3)2]+ 97903 97902 21Pr(NO3)36H2O S6
[(CuL)Pr(NO3)2]+ 62196 62196 11
[(CuL)2Nd(NO3)2]+ 98001 98001 21Nd(NO3)36H2O S7
[(CuL)Nd(NO3)2]+ 62295 62294 11
[(CuL)2Sm(NO3)2]+ 99002 99002 21Sm(NO3)36H2O S8
[(CuL)Sm(NO3)2]+ 63296 63296 11
Table S4 Comparison of HOMO-LUMO gap with the overall electrochemical shift in 11 adducts
Complex Relative stabilization of HOMO-LUMO gap (max) with
respect to [CuL]+K+
(meV)
Expected shift with respect to [CuL]+K+
1198981198901198811 119890
= 119898119881
[E12 (ox) - E12 (red)] =E12 observed from
DPV (V)
Relative shift of E12 with respect to
[CuL]+K+
(mV)
[CuL]+K+ (943-943) = 0 0466-(-1487) =1953 1953-1953 = 0
[CuL]+Na+ (4868-943) = 3925 0487-(-1412) =1899 1953-1899 = 54
[CuL]+Li+ (19920-943) = 18977 0555-(-1207) = 1762 1953-1762 = 191
[CuL]+Ca2+ (25807-943) = 24864 0589-(-1111) = 1700 1953-1700 = 253
[CuL]+Mg2+ (28543-943) = 27600 0623-(-1107) = 1730 1953-1730 = 223
21
Table S5 Summary of UV-Vis and electrochemical properties of complexes 1 and 2
Complex 1 [CuL]+10 equiv
K+
Complex 2 [CuL]+10 equiv
Zn2+
max ( LMCT) nm 3655 362 344 nm 3325
E12 (ox) (V) from
DPV
0493 0898 0466 0913 0471 0612
0920
0652 0784
E12 (red) (V) from
DPV
-1175 (hump) -
1459
-1487 -0875 (hump)
-1011 -1477
Not done
15
Fig S23 Correlation of the shift of oxidation peak potential with the change of molar extinction
coefficient of [CuL] in acetonitrile upon incremental addition of aquous acetonirile
Fig S24 Correlation of the shift of oxidation peak potential with the change of molar extinction
coefficient of [CuL]+10 eqv Zn2+ in acetonitrile upon incremental addition of aquous
acetonirile
16
Fig S25 Correlation of the shift of oxidation peak potential with the change of molar extinction
coefficient of [CuL]+10 eqv Mg2+ in acetonitrile upon incremental addition of aquous
acetonirile
Table S1 List of bond lengths (Aring) and bond angles (ordm) of complexes 1 and 2
M = K M = Zn
M(1)O(1) 2020(6) 2000(4)
M(1)O(2) 2179(5) 2279(5)
M(1)O(3) 2012(5) 1986(4)
M(1)O(4) 2184(6)) 2345(5)
M(1)O(5) 2058(6) 2062(5)
M(1)O(6) 2037(5) 2031(5)
Cu(1)O(1) 1920(5) 1909(5)
Cu(1)O(2) 1944(4) 1917(4)
Cu(1)N(1) 2004(6) 1982(6)
Cu(1)N(2) 1937(7) 1913(6)
Cu(2)O(3) 1909(5) 1922(5)
17
Cu(2)O(4) 1937(5) 1896(4)
Cu(2)N(3) 1966(5) 1963(5)
Cu(2)N(4) 1933(7) 1927(5)
O(1)M(1)O(2) 7448(18) 7182(17)
O(1)M(1)O(3) 1567(2) 14831(19)
O(1)M(1)O(4) 891(2) 8456(17)
O(1)M(1)O(5) 1020(2) 1061(2)
O(1)M(1)O(6) 942(2) 954(2)
O(2)M(1)O(3) 8738(19) 8400(18)
O(2)M(1)O(4) 813(2) 7719(17)
O(2)M(1)O(5) 929(2) 9441(18)
O(2)M(1)O(6) 1684(2) 16616(18)
O(3)M(1)O(4) 734(2) 7002(16)
O(3)M(1)O(5) 933(2) 9563(19)
O(3)M(1)O(6) 1028(2) 1058(2)
O(4)M(1)O(5) 1657(2) 16385(18)
O(4)M(1)O(6) 963(2) 9675(18)
O(5)M(1)O(6) 919(2) 943(2)
O(1)Cu(1)O(2) 824(2) 8238(18)
O(1)Cu(1)N(1) 905(2) 902(2)
O(1)Cu(1)N(2) 1693(3) 1690(2)
O(2)Cu(1)N(1) 1633(2) 1656(2)
O(2)Cu(1)N(2) 918(3) 920(2)
N(1)Cu(1)N(2) 974(3) 973(2)
O(2)Cu(2)O(3) 7047(16) 6993(16)
O(2)Cu(2)O(4) 684(2) 7092(17)
O(2)Cu(2)N(3) 982(2) 9683(17)
O(2)Cu(2)N(4) 1134(2) 11492(18)
18
O(3)Cu(2)O(4) 815(2) 8190(18)
O(3)Cu(2)N(3) 903(2) 901(2)
O(3)Cu(2)N(4) 1712(2) 1717(2)
O(4)Cu(2)N(3) 1660(3) 1671(2)
O(4)Cu(2)N(4) 925(3) 932(2)
N(3)Cu(2)N(4) 968(3) 959(2)
Table S2 Correlation of electrochemical response of previously reported 11 metallohost redox-inactive ion adducts derived from bicompartmental macrocyclic ligands containing adjacent N2O2 and 18-crown-6 like cavity with pKa of corresponding metal-aqua complex
[MnL](PF6)+MXn in acetonitrile MXn =
pKa E12 for Mn(IIIII) (V vs SCE)
KPF6 1625 0025LiClO4 1382 0055Ba(OTf)2 1336 0200Ca(OTf)2 1260 0245
Li+(expected)
[Li+(experimental) - Li+(expected)]
0176
0055 - 0176 =-0121
Data plotted from reference [16] of the main text
[NiL]+MXn in acetonitrileMXn =
pKa EPC for Ni(III)(V vs ferrocene)
NaPF6 1477 -165Ca(OTf)2 1260 -142Nd(OTf)3 843a -118Y(OTf)3 804a -122
Y3+(expected)
[Y3+(experimental) - Y3+(expected)]
-113
-122-(-113) =-009
aobtained from ref Data plotted from reference [17] of the main text
19
[56] of main text[CoL] + MXn in DMF MXn =
pKa E12 for Co(III)(V vs ferrocene)
K(OTf) 1625 -158Na(OTf) 1477 -158Ba(OTf)2 1336 -148Sr(OTf)2 1318 -144Ca(OTf)2 1260 -141
Na+(expected)
[Na+(experimental) - Na+(expected)]
-1515
-158 - (-1515)=-0065
Data plotted from reference [18] of the main text
[CuL]+Mn+ in DMSO Mn+=
pKa E12 for Cu(III)(V vs AgAgCl)
K+ 1625 -1277Na+ 1477 -1279Li+ 1382 -1286Ba2+ 1336 -1119Na+(expected)
[Na+(experimental) - Na+(expected)]
Li+(expected)
[Li+(experimental) - Li+(expected)]
-1185-1279-(-1185)=-0094
-1134-1286-(-1134)=-0152
Data plotted from reference [19] of the main text Line is guide for eye
[Mn(N)L] + MXn in acetonitrile MXn =
pKa E12 for Mn(VVI) (V vs ferrocene)
K(OTf) 1625 0616Na(OTf) 1477 0591Ba(OTf)2 1336 0805Sr(OTf)2 1318 0880
Na+(expected)
[Na+(experimental) - Na+(expected)]
0723
0591-0723 =-0132
Data plotted from reference [31] of the main text
20
Table S3 Masses of species obtained with their calculated values
[CuL]+ 10 eqv MXn
salts
Figure Species detected
with charge
Experimental
Mass (mz)
Calculated
Mass
(mz)
[CuL]M
[(CuL)2Li]+ 72116 72114 21Li(ClO4)3H2O S3
[(CuL)Li]+ 36407 36408 11
[(CuL)2Zn(ClO4)]+ 87701 87701 21
[(CuL)2Zn]2+ 39003 39003 21
Zn(ClO4)26H2O S4
[(CuL)Zn(ClO4)]+ 51994 51994 11
[(CuL)2Cd(ClO4)]+ 92698 92698 21
[(CuL)2Cd]2+ 41402 41401 21
Cd(ClO4)26H2O S5
[(CuL)Cd(ClO4)]+ 56991 56991 11
[(CuL)2Pr(NO3)2]+ 97903 97902 21Pr(NO3)36H2O S6
[(CuL)Pr(NO3)2]+ 62196 62196 11
[(CuL)2Nd(NO3)2]+ 98001 98001 21Nd(NO3)36H2O S7
[(CuL)Nd(NO3)2]+ 62295 62294 11
[(CuL)2Sm(NO3)2]+ 99002 99002 21Sm(NO3)36H2O S8
[(CuL)Sm(NO3)2]+ 63296 63296 11
Table S4 Comparison of HOMO-LUMO gap with the overall electrochemical shift in 11 adducts
Complex Relative stabilization of HOMO-LUMO gap (max) with
respect to [CuL]+K+
(meV)
Expected shift with respect to [CuL]+K+
1198981198901198811 119890
= 119898119881
[E12 (ox) - E12 (red)] =E12 observed from
DPV (V)
Relative shift of E12 with respect to
[CuL]+K+
(mV)
[CuL]+K+ (943-943) = 0 0466-(-1487) =1953 1953-1953 = 0
[CuL]+Na+ (4868-943) = 3925 0487-(-1412) =1899 1953-1899 = 54
[CuL]+Li+ (19920-943) = 18977 0555-(-1207) = 1762 1953-1762 = 191
[CuL]+Ca2+ (25807-943) = 24864 0589-(-1111) = 1700 1953-1700 = 253
[CuL]+Mg2+ (28543-943) = 27600 0623-(-1107) = 1730 1953-1730 = 223
21
Table S5 Summary of UV-Vis and electrochemical properties of complexes 1 and 2
Complex 1 [CuL]+10 equiv
K+
Complex 2 [CuL]+10 equiv
Zn2+
max ( LMCT) nm 3655 362 344 nm 3325
E12 (ox) (V) from
DPV
0493 0898 0466 0913 0471 0612
0920
0652 0784
E12 (red) (V) from
DPV
-1175 (hump) -
1459
-1487 -0875 (hump)
-1011 -1477
Not done
16
Fig S25 Correlation of the shift of oxidation peak potential with the change of molar extinction
coefficient of [CuL]+10 eqv Mg2+ in acetonitrile upon incremental addition of aquous
acetonirile
Table S1 List of bond lengths (Aring) and bond angles (ordm) of complexes 1 and 2
M = K M = Zn
M(1)O(1) 2020(6) 2000(4)
M(1)O(2) 2179(5) 2279(5)
M(1)O(3) 2012(5) 1986(4)
M(1)O(4) 2184(6)) 2345(5)
M(1)O(5) 2058(6) 2062(5)
M(1)O(6) 2037(5) 2031(5)
Cu(1)O(1) 1920(5) 1909(5)
Cu(1)O(2) 1944(4) 1917(4)
Cu(1)N(1) 2004(6) 1982(6)
Cu(1)N(2) 1937(7) 1913(6)
Cu(2)O(3) 1909(5) 1922(5)
17
Cu(2)O(4) 1937(5) 1896(4)
Cu(2)N(3) 1966(5) 1963(5)
Cu(2)N(4) 1933(7) 1927(5)
O(1)M(1)O(2) 7448(18) 7182(17)
O(1)M(1)O(3) 1567(2) 14831(19)
O(1)M(1)O(4) 891(2) 8456(17)
O(1)M(1)O(5) 1020(2) 1061(2)
O(1)M(1)O(6) 942(2) 954(2)
O(2)M(1)O(3) 8738(19) 8400(18)
O(2)M(1)O(4) 813(2) 7719(17)
O(2)M(1)O(5) 929(2) 9441(18)
O(2)M(1)O(6) 1684(2) 16616(18)
O(3)M(1)O(4) 734(2) 7002(16)
O(3)M(1)O(5) 933(2) 9563(19)
O(3)M(1)O(6) 1028(2) 1058(2)
O(4)M(1)O(5) 1657(2) 16385(18)
O(4)M(1)O(6) 963(2) 9675(18)
O(5)M(1)O(6) 919(2) 943(2)
O(1)Cu(1)O(2) 824(2) 8238(18)
O(1)Cu(1)N(1) 905(2) 902(2)
O(1)Cu(1)N(2) 1693(3) 1690(2)
O(2)Cu(1)N(1) 1633(2) 1656(2)
O(2)Cu(1)N(2) 918(3) 920(2)
N(1)Cu(1)N(2) 974(3) 973(2)
O(2)Cu(2)O(3) 7047(16) 6993(16)
O(2)Cu(2)O(4) 684(2) 7092(17)
O(2)Cu(2)N(3) 982(2) 9683(17)
O(2)Cu(2)N(4) 1134(2) 11492(18)
18
O(3)Cu(2)O(4) 815(2) 8190(18)
O(3)Cu(2)N(3) 903(2) 901(2)
O(3)Cu(2)N(4) 1712(2) 1717(2)
O(4)Cu(2)N(3) 1660(3) 1671(2)
O(4)Cu(2)N(4) 925(3) 932(2)
N(3)Cu(2)N(4) 968(3) 959(2)
Table S2 Correlation of electrochemical response of previously reported 11 metallohost redox-inactive ion adducts derived from bicompartmental macrocyclic ligands containing adjacent N2O2 and 18-crown-6 like cavity with pKa of corresponding metal-aqua complex
[MnL](PF6)+MXn in acetonitrile MXn =
pKa E12 for Mn(IIIII) (V vs SCE)
KPF6 1625 0025LiClO4 1382 0055Ba(OTf)2 1336 0200Ca(OTf)2 1260 0245
Li+(expected)
[Li+(experimental) - Li+(expected)]
0176
0055 - 0176 =-0121
Data plotted from reference [16] of the main text
[NiL]+MXn in acetonitrileMXn =
pKa EPC for Ni(III)(V vs ferrocene)
NaPF6 1477 -165Ca(OTf)2 1260 -142Nd(OTf)3 843a -118Y(OTf)3 804a -122
Y3+(expected)
[Y3+(experimental) - Y3+(expected)]
-113
-122-(-113) =-009
aobtained from ref Data plotted from reference [17] of the main text
19
[56] of main text[CoL] + MXn in DMF MXn =
pKa E12 for Co(III)(V vs ferrocene)
K(OTf) 1625 -158Na(OTf) 1477 -158Ba(OTf)2 1336 -148Sr(OTf)2 1318 -144Ca(OTf)2 1260 -141
Na+(expected)
[Na+(experimental) - Na+(expected)]
-1515
-158 - (-1515)=-0065
Data plotted from reference [18] of the main text
[CuL]+Mn+ in DMSO Mn+=
pKa E12 for Cu(III)(V vs AgAgCl)
K+ 1625 -1277Na+ 1477 -1279Li+ 1382 -1286Ba2+ 1336 -1119Na+(expected)
[Na+(experimental) - Na+(expected)]
Li+(expected)
[Li+(experimental) - Li+(expected)]
-1185-1279-(-1185)=-0094
-1134-1286-(-1134)=-0152
Data plotted from reference [19] of the main text Line is guide for eye
[Mn(N)L] + MXn in acetonitrile MXn =
pKa E12 for Mn(VVI) (V vs ferrocene)
K(OTf) 1625 0616Na(OTf) 1477 0591Ba(OTf)2 1336 0805Sr(OTf)2 1318 0880
Na+(expected)
[Na+(experimental) - Na+(expected)]
0723
0591-0723 =-0132
Data plotted from reference [31] of the main text
20
Table S3 Masses of species obtained with their calculated values
[CuL]+ 10 eqv MXn
salts
Figure Species detected
with charge
Experimental
Mass (mz)
Calculated
Mass
(mz)
[CuL]M
[(CuL)2Li]+ 72116 72114 21Li(ClO4)3H2O S3
[(CuL)Li]+ 36407 36408 11
[(CuL)2Zn(ClO4)]+ 87701 87701 21
[(CuL)2Zn]2+ 39003 39003 21
Zn(ClO4)26H2O S4
[(CuL)Zn(ClO4)]+ 51994 51994 11
[(CuL)2Cd(ClO4)]+ 92698 92698 21
[(CuL)2Cd]2+ 41402 41401 21
Cd(ClO4)26H2O S5
[(CuL)Cd(ClO4)]+ 56991 56991 11
[(CuL)2Pr(NO3)2]+ 97903 97902 21Pr(NO3)36H2O S6
[(CuL)Pr(NO3)2]+ 62196 62196 11
[(CuL)2Nd(NO3)2]+ 98001 98001 21Nd(NO3)36H2O S7
[(CuL)Nd(NO3)2]+ 62295 62294 11
[(CuL)2Sm(NO3)2]+ 99002 99002 21Sm(NO3)36H2O S8
[(CuL)Sm(NO3)2]+ 63296 63296 11
Table S4 Comparison of HOMO-LUMO gap with the overall electrochemical shift in 11 adducts
Complex Relative stabilization of HOMO-LUMO gap (max) with
respect to [CuL]+K+
(meV)
Expected shift with respect to [CuL]+K+
1198981198901198811 119890
= 119898119881
[E12 (ox) - E12 (red)] =E12 observed from
DPV (V)
Relative shift of E12 with respect to
[CuL]+K+
(mV)
[CuL]+K+ (943-943) = 0 0466-(-1487) =1953 1953-1953 = 0
[CuL]+Na+ (4868-943) = 3925 0487-(-1412) =1899 1953-1899 = 54
[CuL]+Li+ (19920-943) = 18977 0555-(-1207) = 1762 1953-1762 = 191
[CuL]+Ca2+ (25807-943) = 24864 0589-(-1111) = 1700 1953-1700 = 253
[CuL]+Mg2+ (28543-943) = 27600 0623-(-1107) = 1730 1953-1730 = 223
21
Table S5 Summary of UV-Vis and electrochemical properties of complexes 1 and 2
Complex 1 [CuL]+10 equiv
K+
Complex 2 [CuL]+10 equiv
Zn2+
max ( LMCT) nm 3655 362 344 nm 3325
E12 (ox) (V) from
DPV
0493 0898 0466 0913 0471 0612
0920
0652 0784
E12 (red) (V) from
DPV
-1175 (hump) -
1459
-1487 -0875 (hump)
-1011 -1477
Not done
17
Cu(2)O(4) 1937(5) 1896(4)
Cu(2)N(3) 1966(5) 1963(5)
Cu(2)N(4) 1933(7) 1927(5)
O(1)M(1)O(2) 7448(18) 7182(17)
O(1)M(1)O(3) 1567(2) 14831(19)
O(1)M(1)O(4) 891(2) 8456(17)
O(1)M(1)O(5) 1020(2) 1061(2)
O(1)M(1)O(6) 942(2) 954(2)
O(2)M(1)O(3) 8738(19) 8400(18)
O(2)M(1)O(4) 813(2) 7719(17)
O(2)M(1)O(5) 929(2) 9441(18)
O(2)M(1)O(6) 1684(2) 16616(18)
O(3)M(1)O(4) 734(2) 7002(16)
O(3)M(1)O(5) 933(2) 9563(19)
O(3)M(1)O(6) 1028(2) 1058(2)
O(4)M(1)O(5) 1657(2) 16385(18)
O(4)M(1)O(6) 963(2) 9675(18)
O(5)M(1)O(6) 919(2) 943(2)
O(1)Cu(1)O(2) 824(2) 8238(18)
O(1)Cu(1)N(1) 905(2) 902(2)
O(1)Cu(1)N(2) 1693(3) 1690(2)
O(2)Cu(1)N(1) 1633(2) 1656(2)
O(2)Cu(1)N(2) 918(3) 920(2)
N(1)Cu(1)N(2) 974(3) 973(2)
O(2)Cu(2)O(3) 7047(16) 6993(16)
O(2)Cu(2)O(4) 684(2) 7092(17)
O(2)Cu(2)N(3) 982(2) 9683(17)
O(2)Cu(2)N(4) 1134(2) 11492(18)
18
O(3)Cu(2)O(4) 815(2) 8190(18)
O(3)Cu(2)N(3) 903(2) 901(2)
O(3)Cu(2)N(4) 1712(2) 1717(2)
O(4)Cu(2)N(3) 1660(3) 1671(2)
O(4)Cu(2)N(4) 925(3) 932(2)
N(3)Cu(2)N(4) 968(3) 959(2)
Table S2 Correlation of electrochemical response of previously reported 11 metallohost redox-inactive ion adducts derived from bicompartmental macrocyclic ligands containing adjacent N2O2 and 18-crown-6 like cavity with pKa of corresponding metal-aqua complex
[MnL](PF6)+MXn in acetonitrile MXn =
pKa E12 for Mn(IIIII) (V vs SCE)
KPF6 1625 0025LiClO4 1382 0055Ba(OTf)2 1336 0200Ca(OTf)2 1260 0245
Li+(expected)
[Li+(experimental) - Li+(expected)]
0176
0055 - 0176 =-0121
Data plotted from reference [16] of the main text
[NiL]+MXn in acetonitrileMXn =
pKa EPC for Ni(III)(V vs ferrocene)
NaPF6 1477 -165Ca(OTf)2 1260 -142Nd(OTf)3 843a -118Y(OTf)3 804a -122
Y3+(expected)
[Y3+(experimental) - Y3+(expected)]
-113
-122-(-113) =-009
aobtained from ref Data plotted from reference [17] of the main text
19
[56] of main text[CoL] + MXn in DMF MXn =
pKa E12 for Co(III)(V vs ferrocene)
K(OTf) 1625 -158Na(OTf) 1477 -158Ba(OTf)2 1336 -148Sr(OTf)2 1318 -144Ca(OTf)2 1260 -141
Na+(expected)
[Na+(experimental) - Na+(expected)]
-1515
-158 - (-1515)=-0065
Data plotted from reference [18] of the main text
[CuL]+Mn+ in DMSO Mn+=
pKa E12 for Cu(III)(V vs AgAgCl)
K+ 1625 -1277Na+ 1477 -1279Li+ 1382 -1286Ba2+ 1336 -1119Na+(expected)
[Na+(experimental) - Na+(expected)]
Li+(expected)
[Li+(experimental) - Li+(expected)]
-1185-1279-(-1185)=-0094
-1134-1286-(-1134)=-0152
Data plotted from reference [19] of the main text Line is guide for eye
[Mn(N)L] + MXn in acetonitrile MXn =
pKa E12 for Mn(VVI) (V vs ferrocene)
K(OTf) 1625 0616Na(OTf) 1477 0591Ba(OTf)2 1336 0805Sr(OTf)2 1318 0880
Na+(expected)
[Na+(experimental) - Na+(expected)]
0723
0591-0723 =-0132
Data plotted from reference [31] of the main text
20
Table S3 Masses of species obtained with their calculated values
[CuL]+ 10 eqv MXn
salts
Figure Species detected
with charge
Experimental
Mass (mz)
Calculated
Mass
(mz)
[CuL]M
[(CuL)2Li]+ 72116 72114 21Li(ClO4)3H2O S3
[(CuL)Li]+ 36407 36408 11
[(CuL)2Zn(ClO4)]+ 87701 87701 21
[(CuL)2Zn]2+ 39003 39003 21
Zn(ClO4)26H2O S4
[(CuL)Zn(ClO4)]+ 51994 51994 11
[(CuL)2Cd(ClO4)]+ 92698 92698 21
[(CuL)2Cd]2+ 41402 41401 21
Cd(ClO4)26H2O S5
[(CuL)Cd(ClO4)]+ 56991 56991 11
[(CuL)2Pr(NO3)2]+ 97903 97902 21Pr(NO3)36H2O S6
[(CuL)Pr(NO3)2]+ 62196 62196 11
[(CuL)2Nd(NO3)2]+ 98001 98001 21Nd(NO3)36H2O S7
[(CuL)Nd(NO3)2]+ 62295 62294 11
[(CuL)2Sm(NO3)2]+ 99002 99002 21Sm(NO3)36H2O S8
[(CuL)Sm(NO3)2]+ 63296 63296 11
Table S4 Comparison of HOMO-LUMO gap with the overall electrochemical shift in 11 adducts
Complex Relative stabilization of HOMO-LUMO gap (max) with
respect to [CuL]+K+
(meV)
Expected shift with respect to [CuL]+K+
1198981198901198811 119890
= 119898119881
[E12 (ox) - E12 (red)] =E12 observed from
DPV (V)
Relative shift of E12 with respect to
[CuL]+K+
(mV)
[CuL]+K+ (943-943) = 0 0466-(-1487) =1953 1953-1953 = 0
[CuL]+Na+ (4868-943) = 3925 0487-(-1412) =1899 1953-1899 = 54
[CuL]+Li+ (19920-943) = 18977 0555-(-1207) = 1762 1953-1762 = 191
[CuL]+Ca2+ (25807-943) = 24864 0589-(-1111) = 1700 1953-1700 = 253
[CuL]+Mg2+ (28543-943) = 27600 0623-(-1107) = 1730 1953-1730 = 223
21
Table S5 Summary of UV-Vis and electrochemical properties of complexes 1 and 2
Complex 1 [CuL]+10 equiv
K+
Complex 2 [CuL]+10 equiv
Zn2+
max ( LMCT) nm 3655 362 344 nm 3325
E12 (ox) (V) from
DPV
0493 0898 0466 0913 0471 0612
0920
0652 0784
E12 (red) (V) from
DPV
-1175 (hump) -
1459
-1487 -0875 (hump)
-1011 -1477
Not done
18
O(3)Cu(2)O(4) 815(2) 8190(18)
O(3)Cu(2)N(3) 903(2) 901(2)
O(3)Cu(2)N(4) 1712(2) 1717(2)
O(4)Cu(2)N(3) 1660(3) 1671(2)
O(4)Cu(2)N(4) 925(3) 932(2)
N(3)Cu(2)N(4) 968(3) 959(2)
Table S2 Correlation of electrochemical response of previously reported 11 metallohost redox-inactive ion adducts derived from bicompartmental macrocyclic ligands containing adjacent N2O2 and 18-crown-6 like cavity with pKa of corresponding metal-aqua complex
[MnL](PF6)+MXn in acetonitrile MXn =
pKa E12 for Mn(IIIII) (V vs SCE)
KPF6 1625 0025LiClO4 1382 0055Ba(OTf)2 1336 0200Ca(OTf)2 1260 0245
Li+(expected)
[Li+(experimental) - Li+(expected)]
0176
0055 - 0176 =-0121
Data plotted from reference [16] of the main text
[NiL]+MXn in acetonitrileMXn =
pKa EPC for Ni(III)(V vs ferrocene)
NaPF6 1477 -165Ca(OTf)2 1260 -142Nd(OTf)3 843a -118Y(OTf)3 804a -122
Y3+(expected)
[Y3+(experimental) - Y3+(expected)]
-113
-122-(-113) =-009
aobtained from ref Data plotted from reference [17] of the main text
19
[56] of main text[CoL] + MXn in DMF MXn =
pKa E12 for Co(III)(V vs ferrocene)
K(OTf) 1625 -158Na(OTf) 1477 -158Ba(OTf)2 1336 -148Sr(OTf)2 1318 -144Ca(OTf)2 1260 -141
Na+(expected)
[Na+(experimental) - Na+(expected)]
-1515
-158 - (-1515)=-0065
Data plotted from reference [18] of the main text
[CuL]+Mn+ in DMSO Mn+=
pKa E12 for Cu(III)(V vs AgAgCl)
K+ 1625 -1277Na+ 1477 -1279Li+ 1382 -1286Ba2+ 1336 -1119Na+(expected)
[Na+(experimental) - Na+(expected)]
Li+(expected)
[Li+(experimental) - Li+(expected)]
-1185-1279-(-1185)=-0094
-1134-1286-(-1134)=-0152
Data plotted from reference [19] of the main text Line is guide for eye
[Mn(N)L] + MXn in acetonitrile MXn =
pKa E12 for Mn(VVI) (V vs ferrocene)
K(OTf) 1625 0616Na(OTf) 1477 0591Ba(OTf)2 1336 0805Sr(OTf)2 1318 0880
Na+(expected)
[Na+(experimental) - Na+(expected)]
0723
0591-0723 =-0132
Data plotted from reference [31] of the main text
20
Table S3 Masses of species obtained with their calculated values
[CuL]+ 10 eqv MXn
salts
Figure Species detected
with charge
Experimental
Mass (mz)
Calculated
Mass
(mz)
[CuL]M
[(CuL)2Li]+ 72116 72114 21Li(ClO4)3H2O S3
[(CuL)Li]+ 36407 36408 11
[(CuL)2Zn(ClO4)]+ 87701 87701 21
[(CuL)2Zn]2+ 39003 39003 21
Zn(ClO4)26H2O S4
[(CuL)Zn(ClO4)]+ 51994 51994 11
[(CuL)2Cd(ClO4)]+ 92698 92698 21
[(CuL)2Cd]2+ 41402 41401 21
Cd(ClO4)26H2O S5
[(CuL)Cd(ClO4)]+ 56991 56991 11
[(CuL)2Pr(NO3)2]+ 97903 97902 21Pr(NO3)36H2O S6
[(CuL)Pr(NO3)2]+ 62196 62196 11
[(CuL)2Nd(NO3)2]+ 98001 98001 21Nd(NO3)36H2O S7
[(CuL)Nd(NO3)2]+ 62295 62294 11
[(CuL)2Sm(NO3)2]+ 99002 99002 21Sm(NO3)36H2O S8
[(CuL)Sm(NO3)2]+ 63296 63296 11
Table S4 Comparison of HOMO-LUMO gap with the overall electrochemical shift in 11 adducts
Complex Relative stabilization of HOMO-LUMO gap (max) with
respect to [CuL]+K+
(meV)
Expected shift with respect to [CuL]+K+
1198981198901198811 119890
= 119898119881
[E12 (ox) - E12 (red)] =E12 observed from
DPV (V)
Relative shift of E12 with respect to
[CuL]+K+
(mV)
[CuL]+K+ (943-943) = 0 0466-(-1487) =1953 1953-1953 = 0
[CuL]+Na+ (4868-943) = 3925 0487-(-1412) =1899 1953-1899 = 54
[CuL]+Li+ (19920-943) = 18977 0555-(-1207) = 1762 1953-1762 = 191
[CuL]+Ca2+ (25807-943) = 24864 0589-(-1111) = 1700 1953-1700 = 253
[CuL]+Mg2+ (28543-943) = 27600 0623-(-1107) = 1730 1953-1730 = 223
21
Table S5 Summary of UV-Vis and electrochemical properties of complexes 1 and 2
Complex 1 [CuL]+10 equiv
K+
Complex 2 [CuL]+10 equiv
Zn2+
max ( LMCT) nm 3655 362 344 nm 3325
E12 (ox) (V) from
DPV
0493 0898 0466 0913 0471 0612
0920
0652 0784
E12 (red) (V) from
DPV
-1175 (hump) -
1459
-1487 -0875 (hump)
-1011 -1477
Not done
19
[56] of main text[CoL] + MXn in DMF MXn =
pKa E12 for Co(III)(V vs ferrocene)
K(OTf) 1625 -158Na(OTf) 1477 -158Ba(OTf)2 1336 -148Sr(OTf)2 1318 -144Ca(OTf)2 1260 -141
Na+(expected)
[Na+(experimental) - Na+(expected)]
-1515
-158 - (-1515)=-0065
Data plotted from reference [18] of the main text
[CuL]+Mn+ in DMSO Mn+=
pKa E12 for Cu(III)(V vs AgAgCl)
K+ 1625 -1277Na+ 1477 -1279Li+ 1382 -1286Ba2+ 1336 -1119Na+(expected)
[Na+(experimental) - Na+(expected)]
Li+(expected)
[Li+(experimental) - Li+(expected)]
-1185-1279-(-1185)=-0094
-1134-1286-(-1134)=-0152
Data plotted from reference [19] of the main text Line is guide for eye
[Mn(N)L] + MXn in acetonitrile MXn =
pKa E12 for Mn(VVI) (V vs ferrocene)
K(OTf) 1625 0616Na(OTf) 1477 0591Ba(OTf)2 1336 0805Sr(OTf)2 1318 0880
Na+(expected)
[Na+(experimental) - Na+(expected)]
0723
0591-0723 =-0132
Data plotted from reference [31] of the main text
20
Table S3 Masses of species obtained with their calculated values
[CuL]+ 10 eqv MXn
salts
Figure Species detected
with charge
Experimental
Mass (mz)
Calculated
Mass
(mz)
[CuL]M
[(CuL)2Li]+ 72116 72114 21Li(ClO4)3H2O S3
[(CuL)Li]+ 36407 36408 11
[(CuL)2Zn(ClO4)]+ 87701 87701 21
[(CuL)2Zn]2+ 39003 39003 21
Zn(ClO4)26H2O S4
[(CuL)Zn(ClO4)]+ 51994 51994 11
[(CuL)2Cd(ClO4)]+ 92698 92698 21
[(CuL)2Cd]2+ 41402 41401 21
Cd(ClO4)26H2O S5
[(CuL)Cd(ClO4)]+ 56991 56991 11
[(CuL)2Pr(NO3)2]+ 97903 97902 21Pr(NO3)36H2O S6
[(CuL)Pr(NO3)2]+ 62196 62196 11
[(CuL)2Nd(NO3)2]+ 98001 98001 21Nd(NO3)36H2O S7
[(CuL)Nd(NO3)2]+ 62295 62294 11
[(CuL)2Sm(NO3)2]+ 99002 99002 21Sm(NO3)36H2O S8
[(CuL)Sm(NO3)2]+ 63296 63296 11
Table S4 Comparison of HOMO-LUMO gap with the overall electrochemical shift in 11 adducts
Complex Relative stabilization of HOMO-LUMO gap (max) with
respect to [CuL]+K+
(meV)
Expected shift with respect to [CuL]+K+
1198981198901198811 119890
= 119898119881
[E12 (ox) - E12 (red)] =E12 observed from
DPV (V)
Relative shift of E12 with respect to
[CuL]+K+
(mV)
[CuL]+K+ (943-943) = 0 0466-(-1487) =1953 1953-1953 = 0
[CuL]+Na+ (4868-943) = 3925 0487-(-1412) =1899 1953-1899 = 54
[CuL]+Li+ (19920-943) = 18977 0555-(-1207) = 1762 1953-1762 = 191
[CuL]+Ca2+ (25807-943) = 24864 0589-(-1111) = 1700 1953-1700 = 253
[CuL]+Mg2+ (28543-943) = 27600 0623-(-1107) = 1730 1953-1730 = 223
21
Table S5 Summary of UV-Vis and electrochemical properties of complexes 1 and 2
Complex 1 [CuL]+10 equiv
K+
Complex 2 [CuL]+10 equiv
Zn2+
max ( LMCT) nm 3655 362 344 nm 3325
E12 (ox) (V) from
DPV
0493 0898 0466 0913 0471 0612
0920
0652 0784
E12 (red) (V) from
DPV
-1175 (hump) -
1459
-1487 -0875 (hump)
-1011 -1477
Not done
20
Table S3 Masses of species obtained with their calculated values
[CuL]+ 10 eqv MXn
salts
Figure Species detected
with charge
Experimental
Mass (mz)
Calculated
Mass
(mz)
[CuL]M
[(CuL)2Li]+ 72116 72114 21Li(ClO4)3H2O S3
[(CuL)Li]+ 36407 36408 11
[(CuL)2Zn(ClO4)]+ 87701 87701 21
[(CuL)2Zn]2+ 39003 39003 21
Zn(ClO4)26H2O S4
[(CuL)Zn(ClO4)]+ 51994 51994 11
[(CuL)2Cd(ClO4)]+ 92698 92698 21
[(CuL)2Cd]2+ 41402 41401 21
Cd(ClO4)26H2O S5
[(CuL)Cd(ClO4)]+ 56991 56991 11
[(CuL)2Pr(NO3)2]+ 97903 97902 21Pr(NO3)36H2O S6
[(CuL)Pr(NO3)2]+ 62196 62196 11
[(CuL)2Nd(NO3)2]+ 98001 98001 21Nd(NO3)36H2O S7
[(CuL)Nd(NO3)2]+ 62295 62294 11
[(CuL)2Sm(NO3)2]+ 99002 99002 21Sm(NO3)36H2O S8
[(CuL)Sm(NO3)2]+ 63296 63296 11
Table S4 Comparison of HOMO-LUMO gap with the overall electrochemical shift in 11 adducts
Complex Relative stabilization of HOMO-LUMO gap (max) with
respect to [CuL]+K+
(meV)
Expected shift with respect to [CuL]+K+
1198981198901198811 119890
= 119898119881
[E12 (ox) - E12 (red)] =E12 observed from
DPV (V)
Relative shift of E12 with respect to
[CuL]+K+
(mV)
[CuL]+K+ (943-943) = 0 0466-(-1487) =1953 1953-1953 = 0
[CuL]+Na+ (4868-943) = 3925 0487-(-1412) =1899 1953-1899 = 54
[CuL]+Li+ (19920-943) = 18977 0555-(-1207) = 1762 1953-1762 = 191
[CuL]+Ca2+ (25807-943) = 24864 0589-(-1111) = 1700 1953-1700 = 253
[CuL]+Mg2+ (28543-943) = 27600 0623-(-1107) = 1730 1953-1730 = 223
21
Table S5 Summary of UV-Vis and electrochemical properties of complexes 1 and 2
Complex 1 [CuL]+10 equiv
K+
Complex 2 [CuL]+10 equiv
Zn2+
max ( LMCT) nm 3655 362 344 nm 3325
E12 (ox) (V) from
DPV
0493 0898 0466 0913 0471 0612
0920
0652 0784
E12 (red) (V) from
DPV
-1175 (hump) -
1459
-1487 -0875 (hump)
-1011 -1477
Not done
21
Table S5 Summary of UV-Vis and electrochemical properties of complexes 1 and 2
Complex 1 [CuL]+10 equiv
K+
Complex 2 [CuL]+10 equiv
Zn2+
max ( LMCT) nm 3655 362 344 nm 3325
E12 (ox) (V) from
DPV
0493 0898 0466 0913 0471 0612
0920
0652 0784
E12 (red) (V) from
DPV
-1175 (hump) -
1459
-1487 -0875 (hump)
-1011 -1477
Not done