Post on 13-Jan-2016
THERMODYNAMICS OF MOLECULAR RECOGNITION AND DESIGN OF
SUPRAMOLECULAR ARCHITECTURES ON THE BASIS OF CALIXARENES
A.I.Konovalov, V.V.Gorbatchuk, I.S.Antipin
A.E.Arbuzov Institute of Organic and Physical Chemistry, Kazan Kazan State University
Chemistrymolecular supramolecular
Covalent interactions:
intramolecular binding
Covalent interactions:
intramolecular binding
Specific and nonspecific interactions:
intermolecular binding
Specific and nonspecific interactions:
intermolecular binding
atoms →molecules molecules →supermolecules
Supramolecular assemblies
Radicals
Ions
Ion-radicals
A + B → A―B AB + CD →A―B
C―D
Supermolecules
substrate receptor
guest host
OOO O
H H H H
SSS S
OOO O
H H H H
HOOH HO
OH
OHHOOH
HO
R RR
R
CALIX[4]ARENES
OH
OH
t-Bu
S
4
1872 – A.BayerOH
+ H-CHO polymer productsH+
OH
OH
HC
HO
R
OH4
+ R-CHOH+
OH OH
CH2
n
+ H-CHO OH-
n=4-8
+ S8
NaOH
1944 – A.Zinke, E.Zigler
1978 – C.D.Gutsche
1997 – H.Kumagai et al
R
R R
R
OH
OH
HO
HO
R
R R
R
OH
OH
HO
HO
Brouwer, E. B. et al . Phys. Chem. Chem. Phys. 1999, 1, 4043
Brouwer, E. B.; Enright, G. D.; Ratcliffe, C. I.; Facey, G. A.; Ripmeester, J. A. J. Phys. Chem. 1999, 103, 10604
Calixarenes in Action (Eds. L. Mandolini, R. Ungaro), Imperial College Press. – 2000. -250 p.
Problem: ‘Structure – thermodynamic property’ relationship for inclusion of volatile organic compounds by solid hosts
Experimental methodStatic method of GC headspace
analysis
Experimental methodStatic method of GC headspace
analysis
Solid phase
HOST
GUEST
Vapor phase
Experimental data vapor sorption isotherms
Experimental data vapor sorption isotherms
ResultsInclusion stoichiometry, free energy,
cooperativity
ResultsInclusion stoichiometry, free energy,
cooperativityVariation of host and guest molecular structure
Variation of host and guest molecular structure
Electropneumatic dosingB. Kolb, P. Pospisil, T. Borath and M. Auer, J. High Res. Chromatogr. & Chromatogr. Commun., 1979, 2, 283. Activity determinationA. Hussam and P. W. Carr, Anal. Chem., 1985, 57, 793.
Data examplesJ. H. Park, A. Hussam, P. Couasnon, D. Fritz and P. W. Carr, Anal. Chem., 1987, 59, 1970.
Electropneumatic dosingB. Kolb, P. Pospisil, T. Borath and M. Auer, J. High Res. Chromatogr. & Chromatogr. Commun., 1979, 2, 283. Activity determinationA. Hussam and P. W. Carr, Anal. Chem., 1985, 57, 793.
Data examplesJ. H. Park, A. Hussam, P. Couasnon, D. Fritz and P. W. Carr, Anal. Chem., 1987, 59, 1970.
ELECTROPNEUMATIC VALVE
SPLITTER
FUSED SILICA COLUMN
VIAL WITH SAMPLE
THERMOSTATE
DEVICE OF STATIC HEADSPACE GAS CHROMATOGRAPHIC ANALYSIS
solid phase binding of vapors in comparable conditions
0.00
0.50
1.00
1.50
2.00
0.00 0.50 1.00
Guest activity, P/P0
YS
, mo
l gue
st /
mo
l ho
st MeOHn-PrOHEtCN
0.0
0.4
0.8
1.2
1.6
0.0 0.5 1.0
P/P0
YS; m
ol g
uest
/mol
hos
t CCl4CHCl3CH3NO2
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
0.0 0.2 0.4 0.6 0.8 1.0
P/P0
YS; m
ol g
uest
/mol
hos
t С6Н6CHCl3Dioxane
0.0
1.0
2.0
3.0
4.0
5.0
6.0
0.0 0.5 1.0
P/P0
YS
; m
ol g
uest/m
ol h
ost TolueneBenzeneCHCl3CCl4
Isotherms
T=298 K
OOO OH H HH
HO
OH
OOO OH
HHH S – inclusion stoichiometry
N – cooperativity constant
))С(P/P/(1)SC(P/PYS N0
N0 ))С(P/P/(1)SC(P/PYS N
0N
0 Hill equation
inclusion threshold:50.0
1
0
ln)/ln( aRTdYPPRTG OC = RT(lnC)/N
- inclusion free energy
p-tert-Butylcalix[4]arene
1:1 host-guest complex of p-tert-butylcalix[4]arene with fluorobenzene
Brouwer, E. B.; Udachin, K. A.; Enright, G. D.; Ripmeester J. A. et al Chem. Commun. 2001, 565
Brouwer, E. B et al Phys. Chem. Chem. Phys. 1999, 1, 4043
-10
-5
0
5
10
15
20
0 10 20 30 40 50
MRD, cm3/mol
G
solv, k
J/m
ol
5
41
32
25
1718
43
20
2419
21
26
4427
28
29
30
3133,34
3645
3738
4039
46
1613,14
12,15
11
10
9
42 8
76
4
3
22
1
Solvents: alkanes and cycloalkanes
c-C8H1646
c-C7H1445
c-C6H1244
c-C5H1043
c-C4H842
1,2,4-C6H3Cl341
AmCOOMe40
2-Heptanone39
C6H5Br38
c-C6H11Cl37
c-C6H11NH236
BuCOOMe35
MeCOOBu34
C6H5Cl33
C6H5CH332
n-BuCOMe31
c-C6H11OH30
1-BuBr29
n-BuCOMe28
C6H5OH27
MeCOOPr26
CCl425
C6H624
1-BuCl23
Cl2C=CHCl22
Furfural21
PrCOMe20
C5H5N19
EtI18
1-PrSH17
(MeCO)2O16
Et2O15
MeCOOEt14
EtCOOMe13
1-BuOH12
CS211
EtCOMe10
CHCl39
THF8
MeI7
EtBr6
1-PrOH5
MeCOOMe4
Me2CO3
EtOH2
MeOH1
Gsolv, kJ/mol = -0.702 MRD + 14.0
R=0.9910, n=46, =1.1
B.N.Solomonov, V.V.Gorbatchuk,A.I. Konovalov. Zh. Obsch. Khim. 1981, Vol. 51, P.2688-2693.
-Hsolv / kJ/mol = 5.09 + 1.03 MRD
n=102, r=0.994, =1.56
0.00
0.20
0.40
0.60
0.80
1.00
1.20
1.40
0.0 10.0 20.0 30.0
MR D , cm3/mol
S, m
ol g
ue
st/
mo
l ho
st
1:1
1
8
76
5
4
32
1 CH3OH
14 c-Hexane 20 C6H5OCH3
2 CH3CN
15 n-Hexane 21 n-Heptane
3 EtOH
16 Pinacolone 22 o-Xylene
5 EtCN
17 Toluene 23 C6H5Et
6 (CH3)2CO
18 t-BuOAc 24 n-Octane
7 n-PrOH
8 CHCl39 1,4-Dioxane
10 n-Pentane11 n-BuCl12 C6H6
13 CCl4
19 C6H5NO2 25 n-Nonane0,0
0,5
1,0
1,5
2,0
2,5
0 10 20 30 40 50
MRD, cm3/mol
ST
OIC
HIO
ME
TR
Y,
mo
l g
ue
st
/ m
ol h
ost
15
12
1811
10 1416
19
133 17
20
8
76
5
2
1
21
22
23
24 25
14
2 : 1 guest / host
1 : 1
1 : 2
S~1~ const
V. V. Gorbatchuk, A. G. Tsifarkin, I. S. Antipin, B. N. Solomonov and A.
I. Konovalov, Mendeleev Commun., 1999, 11
Stoichiometry - guest size
1 MeOH 5 Me2CO2 MeCN 6 CH2Cl23 MeNO2 7 CHCl34 EtCN 8 CCl4
Lit.data (X-ray)
V. V. Gorbatchuk, A. G. Tsifarkin, I. S. Antipin, B. N. Solomonov, A. I. Konovalov, P.Lhotak, I.Stibor J. Phys. Chem.B. , 2002, 106(23); 5845-5851
p-tert-Butylcalix[4]arene
1:1 host-guest complex of p-tert-butylcalix[4]arene with fluorobenzene
Brouwer, E. B.; Udachin, K. A.; Enright, G. D.; Ripmeester J. A.; Ooms, K. J.; Halchuk P. A. Chem. Commun. 2001, 565
Brouwer, E. B.; Gougeon, R. D. M.; Hirschinger, J.; Udachin, K. A.; Harris, R. K.;Enright, G. D.; Ripmeester, J. A. Phys. Chem. Chem. Phys. 1999, 1, 4043
All-trans n-hexane, 1-chlorobutane, 1,4-dichlorobutane and 1,4 dichlorobenzene
All-trans n-hexane, 1-heptanol, 1-octanol and dodecane
K. A. Udachin et al. /J. Supramol. Chem. 1 (2001) 97–100
0.00
0.20
0.40
0.60
0.80
1.00
1.20
1.40
0.0 10.0 20.0 30.0
MR D , cm3/mol
S, m
ol g
ue
st/
mo
l ho
st
1:1
1
8
76
5
4
32
1 CH3OH
14 c-Hexane 20 C6H5OCH3
2 CH3CN
15 n-Hexane 21 n-Heptane
3 EtOH
16 Pinacolone 22 o-Xylene
5 EtCN
17 Toluene 23 C6H5Et
6 (CH3)2CO
18 t-BuOAc 24 n-Octane
7 n-PrOH
8 CHCl39 1,4-Dioxane
10 n-Pentane11 n-BuCl12 C6H6
13 CCl4
19 C6H5NO2 25 n-Nonane0,0
0,5
1,0
1,5
2,0
2,5
0 10 20 30 40 50
MRD, cm3/mol
ST
OIC
HIO
ME
TR
Y,
mo
l g
ue
st
/ m
ol h
ost
15
12
1811
10 1416
19
133 17
20
8
76
5
2
1
21
22
23
24 25
14
2 : 1 guest / host
1 : 1
1 : 2
S~1~ const
V. V. Gorbatchuk, A. G. Tsifarkin, I. S. Antipin, B. N. Solomonov and A.
I. Konovalov, Mendeleev Commun., 1999, 11
Stoichiometry - guest size
1 MeOH 5 Me2CO2 MeCN 6 CH2Cl23 MeNO2 7 CHCl34 EtCN 8 CCl4
Lit.data (X-ray)
V. V. Gorbatchuk, A. G. Tsifarkin, I. S. Antipin, B. N. Solomonov, A. I. Konovalov, P.Lhotak, I.Stibor J. Phys. Chem.B. , 2002, 106(23); 5845-5851
Akdas, H.; Bringel, L.; Graf, E.; Hosseini, M. W.; Mislin, G.; Pansanel, J.; de Cian, A.; Fischer, J. Tetrahedron Lett. 1998, 39, 2311
0.00
0.50
1.00
1.50
2.00
2.50
3.00
0 10 20 30 40
MR D , cm3/mol
S, m
ol g
uest
/ mo
l ho
st
2:1
1:1
112
11
1098
7
6
5
4
3
2
1 MeOH 7 CHCl32 MeCN 8 1,4-
Dioxane
3 EtCN 9 Pyridine
4 Me2CO 10 C6H6
5 1-PrOH 11 CCl46 1-PrCN 12 Et3N
HO
OH
Stoichiometry - guest size
V. V. Gorbatchuk, A. G. Tsifarkin, I. S. Antipin, B. N. Solomonov, A. I. Konovalov, J. Seidel, F. Baitalov, J. Chem.Soc. Perkin Trans. 2, 2000, N11, P.2287-2294
L. J. Barbour, S. A. Bourne, M. R. Caira, L. R. Nassimbeni, E. Weber, K. Skobridis and A. Wierig, Supramol. Chem., 1993, 1, 331
0.00
0.50
1.00
1.50
2.00
0.00 0.50 1.00
Guest activity, P/P0
YS
, mo
l gue
st /
mo
l ho
st MeOHn-PrOHEtCN
0.0
0.4
0.8
1.2
1.6
0.0 0.5 1.0
P/P0
YS; m
ol g
uest
/mol
hos
t CCl4CHCl3CH3NO2
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
0.0 0.2 0.4 0.6 0.8 1.0
P/P0
YS; m
ol g
uest
/mol
hos
t С6Н6CHCl3Dioxane
0.0
1.0
2.0
3.0
4.0
5.0
6.0
0.0 0.5 1.0
P/P0
YS
; m
ol g
uest/m
ol h
ost TolueneBenzeneCHCl3CCl4
Isotherms
T=298 K
OOO OH H HH
HO
OH
OOO OH
HHH S – inclusion stoichiometry
N – cooperativity constant
))С(P/P/(1)SC(P/PYS N0
N0 ))С(P/P/(1)SC(P/PYS N
0N
0 Hill equation
inclusion threshold:50.0
1
0
ln)/ln( aRTdYPPRTG OC = RT(lnC)/N
- inclusion free energy
N Guest MRD Gc(vap) Gc(vap) Gc(vap)
1 MeOH 8.3 -5.7 -4.8 -6.5
2 CH3CN 11.1 -9.3 -7.3 -7.93 EtOH 12.9 -8.6 * -6.94 EtCN 16 -12.1 -8.1 -9.5
5 Me2CO 16.1 -4.8 -4.2 -4.9
6 CH2Cl2 16.3 -10.3 -3.5 -7 1-PrOH 17.5 -11.4 * -9.78 n-PrCN 20.4 -11.9 * -11.1
9 CHCl3 21.3 -5.6 -4.5 -5.1
10 C5H5N 24.1 -17.0 * -13.3
11 C6H6 26.2 -12.4 * -6.5
12 CCl4 26.4 -8.6 -5.1 -5.8
13 c-C6H12 27.7 -10.5 * *14 n-C6H14 29.9 -8.7 * *15 Pinacolone 30 -9.9 * *
16 PhCH3 31.1 -13.7 * *17 t-BuOAc 31.7 -10.6 * *
18 PhOCH3 32.9 -19.8 * *
19 Et3N 33.8 -12.4 * -8.5
20 n-C7H16 34.5 -11.8 * *
21 o-C6H4Me2 35.9 -14.5 * *
22 n-C8H18 39.2 -14.2 * *
23 n-C9H20 43.8 -15.3 * *
24 MeNO2 12.9 * -9.3 -25 Dioxane 21.7 - * -10.0
HO
OH
* no binding
- not determined
0.0
5.0
10.0
15.0
20.0
25.0
0 10 20 30 40 50
MR D, cm3/mol
G
c(va
p),
kJ/m
ol
1
22
21
20
19
18
17
16
14
13
12
11
10
9
87
23
5
4
3
2
156
Guest vapor
solid host-guest compound
Gc(
vap)
OOO OH H HH
Benzene, toluene, o-xyleneAlcohols, ketones, esters, anisoleNitriles, pyridine, triethylamine
polychloromethanes
n-alcanes, cyclohexane
0.0
5.0
10.0
15.0
20.0
25.0
0 10 20 30 40 50
MR D, cm3/mol
G
c (va
p),
kJ/
mo
l
1
22
21
2019
18
17
16
14
13
12
11
10
9
87
23
5
4
3
2
156
Guest vapor
solid host-guest compound
Gc(
vap)
OOO OH H HH
Guest vapor
toluene solution
Gso
lv
Alcohols, ketones, esters, anisoleNitriles, pyridine, triethylamine
polychloromethanes
Benzene, toluene, o-xylene
n-alcanes, cyclohexane
-6
-4
-2
0
2
4
6
8
10
12
14
0 10 20 30 40 50
MR D , cm3/mol
G
solv
, kJ/
mol
1
22
21
20
19
18
17
16
14
1312
11
10
9
8
76
5
3
2
154
23
Alcohols, ketones, esters, anisoleNitriles, pyridine, triethylamine
polychloromethanes
Benzene, toluene, o-xylene
n-alcanes, cyclohexane
0.0
5.0
10.0
15.0
20.0
25.0
-5.0 0.0 5.0 10.0 15.0
G solv , kJ/mol
G
c (va
p), k
J/m
ol
1
19
23
22
21
20
18
16
15
14
13
12
9
87
6
5
4
32
17
G c (vap) = G solv
6
10
11
Guest vapor
solution
Gso
lv
=+G cav
G int
Solvation process
cavity formation interaction
Gtr
ans
toluene solution
solid host-guest compound
Alcohols, ketones, esters, anisoleNitriles, pyridine, triethylamine
polychloromethanes
Benzene, toluene, o-xylene
n-alcanes, cyclohexane
-12
-10
-8
-6
-4
-2
0
0 10 20 30 40 50
MR D , см3/моль
Gtr
ans, к
Дж
/мо
ль
1
22
21
20
1918
17
1614
13
12
11
10
9
8
7
6
5
4
3
2
15
23
OOO OH H HH
0.0
2.0
4.0
6.0
8.0
10.0
0 5 10 15 20 25 30
MR D, cm3/mol
G
c (va
p), k
J/m
ol
1
12
96
5
24
2
4
MeOH, acetone
MeCN, EtCN
polychloromethanes
nitromethane
Guest vapor
Gc(
vap)
solid host-guest compound
-9.0
-8.0
-7.0
-6.0
-5.0
-4.0
-3.0
-2.0
-1.0
0.0
0 5 10 15 20 25 30
MR D , cm3/mol
Gtr
ans, k
J/m
ol
1
129
6
5
24
2
4
Gtr
ans
toluene solution
solid host-guest compound
MeOH, acetone
MeCN, EtCN
polychloromethanes
nitromethane
Gtrans /kJ mol-1 = -12.24 + 0.568MRD
(n = 7, r = 0.972, RSD = 0.6)V. V. Gorbatchuk, A. G. Tsifarkin, I. S. Antipin, B. N. Solomonov, A. I. Konovalov, P.Lhotak, I.Stibor J. Phys. Chem.B. , 2002, 106(23); 5845-5851
-6
-5
-4
-3
-2
-1
0
1
2
0 10 20 30 40
MR D , cm3/mol
Gtr
ans -0
.236
G
HP
hOH
, kJ/
mol
1
7
58
12
1911
1043
2
9
25
Alcohols, acetone, dioxane
MeCN, EtCN, PrCN, pyridine, Et3N
CHCl3, CCl4benzene
Gtrans /kJ mol-1 = -5.58 + 0.200MRD + 0.391GHMeOH (n = 13, r = 0.955, RSD = 0.8)
Gtrans /kJ mol-1 = -5.76 + 0.204MRD + 0.236GHPhOH (n = 13, r = 0.954, RSD = 0.8)
HO
OH
V. V. Gorbatchuk, A. G. Tsifarkin, I. S. Antipin, B. N. Solomonov, A. I. Konovalov, J. Seidel, F. Baitalov, J. Chem.Soc. Perkin Trans. 2, 2000, N11, P.2287-2294
Dr.Gorbatchuk V.V.Prof.Antipin I.S. Dr.Tsifarkin A.G.Dr.Ziganshin M.A.Prof.Solomonov B.N.
Group cooperates withW.Habicher TU Dresden, GermanyJ.Seidel TU BA Freiberg, GermanyI.Stibor, P. Lhotak VSHT Prague, Czech Rep.
Support from RFBR (grants № 00-15-97411, 01-03-32079)