‐ S1 ‐
Construction of Supramolecular Hyperbranched Polymers via
“Tweezering Directed Self-Assembly” Strategy
Yu-Kui Tian,a Zhi-Shuai Yang,a Xiao-Qin Lv,a Ri-Sheng Yao*b and Feng Wang*a
a Key Laboratory of Soft Matter Chemistry, Department of Polymer Science and Engineering, University of Science and Technology of China,
Hefei, Anhui 230026 (P. R. China) Fax: (+86) 551 3606 095; E-mail: [email protected].
b School of Medical Engineering, Hefei University of Technology,
Hefei, Anhui 230009 (P. R. China). E-mail: [email protected]
Supporting Information
1. Materials and Methods S2
2. Synthetic routes to the targeted monomers 1–3 S3
3. UV/Vis titration between 6 and pyrene S27
4. 1H NMR titration between 6 and 7 S28
5. UV/Vis titration experiments for complexes 6/2 and 1/2 S29
6. Molecular recognition studies for the four monotopic compounds S30
7. Complexation studies for 1–3 via step-wise self-assembly pathway S31
8. COSY NMR spectra for the mixture of 1–3 S32
9. DOSY experiments for the linear and hyperbranched supramolecuar polymers S33
10. Stimuli-responsive properties for 5 S34
Electronic Supplementary Material (ESI) for ChemComm.This journal is © The Royal Society of Chemistry 2014
‐ S2 ‐
1. Materials and Methods
Diphenylammonium triflate (DPAT), 2-methyl-3-butyn-2-ol, copper(I) iodide (CuI),
3-bromoacetephenone, N-(3-(dimethylamino)propyl)-N'-ethylcarbodiimide hydrochloride
(EDC·HCl), 4-dimethylamino pyridine (DMAP), and trimethylsilylacetylene were reagent
grade and used as received. [Pt(tpy)Cl](PF6),[S1]
Benzo-21-crown-7 acid,[S2] compound 8,[S2]
[Au(C^N^C)Cl] (C^N^C = 2,6-diphenylpyridine),[S3] 4-ethenylphenol,[S4] and
4-((10-bromodecyl)oxy)benzaldehyde[S5] were synthesized according to the previously
reported procedures. Compounds 6, 9, 10 and 4-[(12-hydroxydodecyl)oxy]benzaldehyde were
synthesized according to our previously reported paper.[S6] Other reagents and solvents were
employed as purchased. 1H NMR spectra were collected on a Varian Unity INOVA-300 or INOVA-400
spectrometer with TMS as the internal standard. 13C NMR spectra were recorded on a Varian
Unity INOVA-400 spectrometer at 100 MHz. Two-dimensional COSY experiments were
performed on a Varian Unity INOVA-400 MHz spectrometer. Electrospray ionization mass
spectra (ESI-MS) were obtained on a Bruker Esquire 3000 plus mass spectrometer
(Bruker-Franzen Analytik GmbH Breman, Germany) equipped with an ESI interface and ion
trap analyzer. Time-of-flight mass spectra (TOF-MS) were obtained on matrix-assisted laser
desorption/ionization TOF/TOF MS (autoflex speed TOF/TOF, Bruker). UV/Vis spectra were
recorded on a UV-1800 Shimadzu spectrometer.
‐ S3 ‐
2. Synthetic route to the targeted monomers 1–3
Scheme S1. Synthetic route to monomer 1.
Scheme S2. Synthetic route to monomers 2.
‐ S4 ‐
O
O
OO
O
O
OO5
3PF6
51) HCl
2) NH4PF6
BrO
H
O
5
1) 1-Butylamine, CH3OH
2) NaBH4, CH3OHBr
O5
1,3,5-Benzenetricarboxylic acid, 1,1,3,3-tetramethylguanidine, DMSO
_
15
3
O
NH2
NH2
H2N
3) (Boc)2O, CH2Cl2
NBoc
5
O
O
OO
O
O
OO55
16
O
N
N
N
5
Boc
Boc
Boc
H25
H24 H23
Scheme S3. Synthetic route to monomer 3.
2.1. Synthesis of compound 11
Benzo-21-crown-7 acid (520 mg, 1.30 mmol), compound 10 (620 mg, 1.30 mmol),
EDC·HCl (600 mg, 3.16 mmol) and DMAP (50.0 mg, 0.41 mmol) in 30 mL CH2Cl2 were
placed in a 50 mL round-bottom flask and the mixture was stirred for 24 hours at room
temperature. After the reaction was complete, the solvent was extracted with H2O/CH2Cl2.
The combined organic extracts were removed with a rotary evaporator and the residue was
purified by flash column chromatography (ethyl acetate/CH2Cl2, 1 : 2 v/v as the eluent) to
provide compound 11 as a colorless oil (788 mg, 66%). The 1H NMR spectrum of compound
11 is shown in Figure S1. 1H NMR (300 MHz, CDCl3, room temperature) (ppm): 8.29 (s,
2H), 8.21 (d, J = 7.8 Hz, 2H), 7.86 (s, 2H), 7.70 (d, J = 8.7 Hz, 2H), 7.65 (m, 1H), 7.56 (m,
3H), 7.48 (t, J = 7.7 Hz, 2H), 7.04 (d, J = 8.7 Hz, 2H), 6.86 (d, J = 8.5 Hz, 1H), 4.28 (t, J =
6.6 Hz, 2H), 4.24–4.15 (m, 4H), 4.04 (t, J = 6.5 Hz, 2H), 3.94 (m, 4H), 3.80 (m, 4H), 3.74 (m,
4H), 3.67 (m, 8H), 3.15 (s, 2H), 1.89–1.72 (m, 6H), 1.31 (s, 14H). The 13C NMR spectrum of
compound 11 is shown in Figure S2. 13C NMR (75 MHz, CDCl3, room temperature) δ (ppm):
166.4, 160.2, 156.4, 152.8, 150.0, 148.2, 139.7, 132.6, 130.7, 130.5, 128.8, 127.7, 123.8,
123.3, 122.5, 116.9, 115.1, 114.6, 112.2, 83.7, 71.3, 71.2, 71.1, 71.0, 70.6, 69.6, 69.5, 69.3,
‐ S5 ‐
69.1, 68.2, 65.0, 60.4, 29.6, 29.5, 29.4, 29.3, 29.2, 28.8, 26.0. ESI–MS m/z: [M + H]+,
C58H68NO10, 938.48358.
14.19
6.65
1.73
6.62
4.22
3.95
3.84
2.29
3.76
2.18
1.07
2.00
1.92
2.90
1.26
1.91
1.94
1.75
1.85
1.25
1.31
1.68
1.73
1.75
1.77
1.81
1.83
3.15
3.67
3.73
3.75
3.79
3.80
3.94
4.02
4.04
4.19
4.21
4.22
4.25
4.28
4.30
6.85
6.88
7.03
7.06
7.26
7.48
7.51
7.54
7.55
7.56
7.59
7.67
7.69
7.71
7.86
8.19
8.22
8.29
Figure S1. 1H NMR spectrum (300 MHz, CDCl3, room temperature) of compound 11.
30405060708090105120135150165
26.05
28.78
29.31
29.42
29.55
29.58
64.99
69.08
69.30
69.50
69.65
70.55
71.00
71.03
71.11
71.14
71.23
71.34
83.70
112.20
114.58
115.11
116.86
122.51
123.28
123.83
127.67
128.29
128.79
130.49
130.72
132.60
139.73
148.22
149.95
152.81
156.45
160.23
166.42
Figure S2. 13C NMR spectrum (75 MHz, CDCl3, room temperature) of compound 11.
‐ S6 ‐
Figure S3. Electrospray ionization spectrum of compound 11.
2.2. Synthesis of compound 6
Compound 10 (150 mg, 0.27 mmol), [Pt(tpy)Cl](BF4) (430 mg, 0.60 mmol), CuI (10.0 mg,
0.05 mmol) and NEt3 (5 mL) in 50 mL CH2Cl2 were stirred at room temperature for 48 hours
under nitrogen atmosphere. The mixture was evaporated under reduced pressure and the
residue was purified by flash column chromatograph (acetone/CH2Cl2, 1 : 20 v/v as the eluent)
to afford a yellow solid. The solid was dissolved in CH3CN and the NH4PF6 was added. The
resulting solution was stirred at room temperature for 1 hour and washed with H2O/CH2Cl2.
The organic extracts were dried over anhydrous Na2SO4 and evaporated with a rotary
evaporator to afford compound 6 as a red solid (300 mg, 54%). Mp: 210.0−213.5 oC. The 1H
NMR spectrum of compound 6 is shown in Figure S4. The aromatic protons on 6 display
severe signal broadening phenomenaon in 1H NMR spectrum, which probably results from
the irregular capture of one diphenylpyridine unit by another molecular tweezer unit to form
disordered self-recognition structures. The 13C NMR spectrum of compound 6 is shown in
Figure S5. 13C NMR (100 MHz, CDCl3, room temperature) δ (ppm): 166.6, 165.1, 160.4,
‐ S7 ‐
157.7, 155.8, 153.5, 153.0, 138.4, 132.3, 131.9, 130.3, 129.7, 128.4, 127.8, 125.5, 125.3,
121.8, 120.6, 115.3, 111.5, 102.8, 98.1, 68.2, 63.0, 47.6, 36.8, 36.0, 32.8, 31.9, 30.2, 30.0,
29.7, 29.6, 29.5, 29.4, 29.3, 26.2, 25.8. ESI–MS m/z: [M – 2PF6]2+, C93H109N7O2Pt2, 873.4.
1.02.03.04.05.06.07.08.09.010.0
17.35
12.86
2.10
2.00
17.61
9.20
3.22
1.05
Figure S4. 1H NMR spectrum (300 MHz, CDCl3, room temperature) of compound 6.
29.44
29.61
29.68
29.98
30.21
36.01
47.63
63.00
68.19
98.10
102.83
115.32
120.65
121.79
125.29
125.53
127.75
128.40
129.71
130.32
131.86
132.26
138.40
153.02
153.47
155.84
157.69
160.45
165.10
166.55
Figure S5. 13C NMR spectrum (100 MHz, CDCl3, room temperature) of compound 6.
‐ S8 ‐
212.1 360.4 540.6
873.4
1254.6
1719.7
1891.6
2654.1
+MS, 0.0-0.1min (#2-#7)
0.00
0.25
0.50
0.75
1.00
1.25
6x10Intens.
500 1000 1500 2000 2500 m/z
Figure S6. Electrospray ionization spectrum of compound 6.
2.3. Synthesis of monomer 1
Compound 11 (230 mg, 0.25 mmol), [Pt(tpy)Cl](BF4) (390 mg, 0.54 mmol), CuI (10.0 mg,
0.06 mmol) and NEt3 (3 mL) in 30 mL CH2Cl2 were stirred at room temperature for 48 hours
under nitrogen atmosphere. After the reaction was complete, the solvent was evaporated under
reduced pressure and the residue was purified by flash column chromatograph
(acetone/CH2Cl2, 1 : 20 v/v as the eluent) to afford a red solid. The solid was dissolved in
CH3CN and then NH4PF6 was added. The result solution was stirred at room temperature for
1 hour, and then washed with H2O/CH2Cl2. The organic extracts were dried over anhydrous
Na2SO4 and evaporated with a rotary evaporator to afford compound 1 as a red solid (310 mg,
51%). Mp: 180.1−182.8 oC. The 1H NMR spectrum of compound 1 is shown in Figure S7.
Similar to 6, the aromatic protons on 1 also display signal broadening phenomena in 1H NMR
spectrum, which probably results from the irregular capture of one diphenylpyridine unit by
another molecular tweezer unit to form disordered self-recognition structures. The 13C NMR
spectrum of compound 1 is shown in Figure S8. 13C NMR (100 MHz, CDCl3, room
temperature) δ (ppm): 166.4, 165.1, 160.5, 157.7, 155.8, 153.5, 153.0, 152.8, 148.2, 139.2,
138.4, 132.2, 127.7, 125.3, 123.9, 123.3, 122.6, 121.8, 120.6, 115.4, 114.7, 114.0, 112.3,
102.8, 97.8, 71.2, 71.1, 71.0 70.9, 70.5, 69.6, 69.5, 69.3, 69.0, 68.2, 65.0, 36.8, 36.0, 33.8,
‐ S9 ‐
31.9, 30.3, 30.2, 30.0, 29.7, 29.6, 29.5, 29.4, 29.3, 29.1, 28.9, 28.8, 26.2, 26.1, 22.7.
MALDI–TOF MS m/z: [M – PF6]+, C112H135PF6N7O10Pt2, 2272.9208.
1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
22.83
3.46
2.52
7.71
3.88
3.70
3.97
2.28
4.00
2.11
1.26
2.75
3.99
4.88
1.68
2.09
1.79
1.95
1.70
3.62
3.64
3.18
Figure S7. 1H NMR spectrum (300 MHz, CDCl3, room temperature) of monomer 1.
2535455565758595110125140155170
22.67
26.09
26.20
28.80
28.94
29.14
29.34
29.35
29.44
29.49
29.60
29.67
30.00
30.24
30.33
31.90
33.80
36.02
36.80
65.02
68.20
69.03
69.26
69.48
69.63
70.53
70.92
70.95
70.99
71.00
71.11
71.19
112.34
114.05
114.68
115.37
120.62
121.78
123.33
123.90
125.32
127.74
132.20
148.22
152.83
153.02
153.49
157.69
166.44
Figure S8. 13C NMR spectrum (100 MHz, CDCl3, room temperature) of monomer 1.
‐ S10 ‐
Figure S9. MALDI–TOF spectrum of monomer 1.
2.4. Synthesis of compound 12
4-Ethynylphenol (500 mg, 4.23 mmol) and K2CO3 (2.00 g, 14.5 mmol) were placed in a
150 mL round-bottom flask. 1,10-Dibromodecane (6.00 g, 20.0 mmol) in CH3CN (100 mL)
was added and the resulting mixture was stirred at 50 oC for 36 hours. The solvent was
evaporated under reduced pressure and the residue was extracted with H2O/CH2Cl2. After the
combined organic extracts were dried over anhydrous Na2SO4 and evaporated with a rotary
evaporator, the residue was purified by flash column chromatography (petroleum ether as the
eluent) to afford compound 12 as a yellow solid (1.10 g, 77%). Mp: 66.5−68.7 oC. The 1H
NMR spectrum of compound 12 is shown in Figure S10. 1H NMR (300 MHz, CDCl3, room
temperature) (ppm): 7.39 (d, J = 8.3 Hz, 2H), 6.81 (d, J = 8.2 Hz, 2H), 3.93 (t, J = 6.4 Hz,
2H), 3.39 (t, J = 6.8 Hz, 2H), 2.97 (s, 1H), 1.91–1.68 (m, 4H), 1.40 (m, 4H), 1.29 (m, 8H).
The 13C NMR spectrum of compound 12 is shown in Figure S11. 13C NMR (75 MHz, CDCl3,
room temperature) δ (ppm): 159.5, 133.6, 114.4, 113.9, 83.8, 75.7, 68.0, 34.1, 32.8, 29.4, 29.3,
29.2, 28.8, 28.2, 26.0. EI–MS m/z: [M – e]+, C18H25O81Br, 338.1063.
‐ S11 ‐
8.57
4.15
4.33
0.93
2.15
2.11
2.10
2.00
1.40
1.73
1.75
1.78
1.81
1.83
1.86
2.97
3.37
3.39
3.41
3.91
3.93
3.95
6.79
6.82
7.38
7.41
Figure S10. 1H NMR spectrum (300 MHz, CDCl3, room temperature) of compound 12.
25.99
28.16
28.75
29.15
29.32
29.36
29.43
32.82
34.07
68.02
75.70
83.77
113.87
114.44
133.56
159.52
Figure S11. 13C NMR spectrum (75 MHz, CDCl3, room temperature) of compound 12.
‐ S12 ‐
Figure S12. Electron ionization spectrum of compound 12.
2.5. Synthesis of compound 7
Compound 12 (80.0 mg, 0.24 mmol), [Au(C^N^C)(Cl)] (100 mg, 0.22 mmol), CuI (9.50
mg, 0.05 mmol) and NEt3 (0.50 mL) in 5 mL CH2Cl2 were stirred at room temperature for 48
hours under nitrogen atmosphere. After the reaction was complete, the solvent was evaporated
under reduced pressure and the residue was purified by flash column chromatograph
(petroleum ether/CH2Cl2, 3 : 1 v/v as the eluent) to afford compound 7 as a yellow solid (120
mg, 72%). Mp: 120.1−122.0 oC. The 1H NMR spectrum of compound 7 is shown in Figure
S13. 1H NMR (300 MHz, CDCl3, room temperature) (ppm): 8.09 (d, J = 7.2 Hz, 2H), 7.84
(t, J = 7.9 Hz, 1H), 7.53 (d, J = 8.0 Hz, 4H), 7.46 (d, J = 8.0 Hz, 2H), 7.38 (t, J = 7.4 Hz, 2H),
7.24 (m, 2H), 6.84 (d, J = 8.2 Hz, 2H), 3.96 (t, J = 6.3 Hz, 2H), 3.40 (t, J = 6.8 Hz, 2H),
1.91–1.71 (m, 4H), 1.42 (m, 4H), 1.30 (m, 8H). The 13C NMR spectrum of compound 7 is
shown in Figure S14. 13C NMR (75 MHz, CDCl3, room temperature) δ (ppm): 166.9, 164.8,
158.2, 149.0, 142.1, 136.6, 133.1, 131.8, 126.6, 125.2, 118.8, 116.8, 114.3, 100.6, 89.3, 68.0,
‐ S13 ‐
34.1, 32.8, 29.5, 29.4, 29.3, 28.8, 28.2, 26.0. MALDI–TOF MS m/z: [M – e]+, C35H35AuBrNO,
761.1443.
Figure S13. 1H NMR spectrum (300 MHz, CDCl3, room temperature) of compound 7.
Figure S14. 13C NMR spectrum (75 MHz, CDCl3, room temperature) of compound 7.
‐ S14 ‐
Figure S15. MALDI–TOF spectrum of compound 7.
2.6. Synthesis of compound 13
Benzo-21-crown-7 acid (3.50 g, 8.75 mmol), 12-iodododecanol (2.50 g, 8.00 mmol),
EDC·HCl (3.00 g, 15.7 mmol) and DMAP (300 mg, 2.45 mmol) in CH2Cl2 (50 mL) were
placed in a 100 mL round-bottom flask and the mixture was stirred for 24 hours at room
temperature. After the reaction was complete, the solvent was extracted with H2O/CH2Cl2.
The combined organic extracts were removed with a rotary evaporator and the residue was
purified by flash column chromatography (ethyl acetate as the eluent) to provide compound
13 as a colorless oil (3.40 g, 61%). The 1H NMR spectrum of compound 13 is shown in
Figure S16. 1H NMR (300 MHz, CDCl3, room temperature) (ppm): δ 7.66 (dd, J = 8.4, 2.0
Hz, 1H), 7.55 (d, J = 2.0 Hz, 1H), 6.87 (d, J = 8.5 Hz, 1H), 4.27 (t, J = 6.7 Hz, 2H), 4.24–4.17
(m, 4H), 3.97–3.90 (m, 4H), 3.84–3.78 (m, 4H), 3.78–3.71 (m, 4H), 3.71–3.63 (m, 8H), 3.19
(t, J = 7.0 Hz, 2H), 1.86–1.69 (m, 4H), 1.37 (m, 4H), 1.28 (m, 12H). The 13C NMR spectrum
of compound 13 is shown in Figure S17. 13C NMR (75 MHz, CDCl3, room temperature) δ
(ppm): 166.4, 152.8, 148.2, 123.8, 123.3, 114.6, 112.2, 71.4, 71.2, 71.1, 71.0, 70.6, 69.6, 69.5,
69.3, 69.1, 65.0, 33.6, 30.5, 29.5, 29.4, 29.3, 28.8, 28.5, 26.0. ESI–MS m/z: [M + H]+,
‐ S15 ‐
C31H52IO9, 695.26501.
Figure S16. 1H NMR spectrum (300 MHz, CDCl3, room temperature) of compound 13.
Figure S17. 13C NMR spectrum (75 MHz, CDCl3, room temperature) of compound 13.
‐ S16 ‐
Figure S18. Electrospray ionization spectrum of compound 13.
2.7. Synthesis of compound 14
4-Ethynylphenol (0.40 g, 3.39 mmol) and K2CO3 (0.70 g, 5.07 mmol) were placed in a 150
mL round-bottom flask. Compound 13 (1.70 g, 2.45 mmol) in CH3CN (40 mL) was added
and the resulting mixture was stirred at 90 oC for 24 hours. The solvent was evaporated under
reduced pressure and the residue was extracted with H2O/CH2Cl2. After the combined organic
extracts were dried over anhydrous Na2SO4 and evaporated with a rotary evaporator, the
residue was purified by flash column chromatography (CH3OH/CH2Cl2, 1 : 20 v/v as the
eluent) to afford compound 14 as a yellow oil (1.40 g, 84%). The 1H NMR spectrum of
compound 14 is shown in Figure S19. 1H NMR (300 MHz, CDCl3, room temperature)
(ppm): 7.65 (m, 1H), 7.55 (d, J = 2.0 Hz, 1H), 7.45–7.37 (m, 2H), 6.91–6.79 (m, 3H), 4.27 (t,
J = 6.7 Hz, 2H), 4.24–4.16 (m, 4H), 3.92–3.97 (m, 6H), 3.84–3.78 (m, 4H), 3.76–3.72 (m,
4H), 3.71–3.63 (m, 8H), 2.99 (s, 1H), 1.76 (m, 4H), 1.49–1.37 (m, 4H), 1.29 (m, 12H). The 13C NMR spectrum of compound 14 is shown in Figure S20. 13C NMR (75 MHz, CDCl3,
room temperature) δ (ppm): 166.4, 159.5, 152.8, 148.2, 133.6, 123.8, 123.3, 114.6, 114.4,
113.8, 112.2, 83.8, 75.7, 71.3, 71.2, 71.1, 71.0, 69.6, 69.5, 69.3, 69.1, 68.0, 65.0, 29.5, 29.4,
29.3, 29.2, 28.8, 26.0. ESI–MS m/z: [M + H]+, C39H57O10, 685.39453.
‐ S17 ‐
1.82.63.44.25.05.86.67.4
13.2
34.
37
4.11
1.03
8.71
4.35
4.26
6.08
4.35
2.23
3.18
2.00
1.13
1.17
1.26
1.29
1.39
1.41
1.44
1.72
1.75
1.77
2.99
3.66
3.68
3.69
3.72
3.74
3.74
3.76
3.80
3.81
3.81
3.82
3.83
3.92
3.93
3.93
3.95
3.96
3.97
4.19
4.21
4.22
4.25
4.27
4.30
6.81
6.83
6.84
6.85
6.88
7.26
7.40
7.40
7.42
7.43
7.55
7.55
7.64
7.64
7.67
7.67
Figure S19. 1H NMR spectrum (300 MHz, CDCl3, room temperature) of compound 14.
30405060708090105120135150165
25.99
26.04
28.77
29.15
29.30
29.37
29.54
68.05
69.09
69.29
69.50
69.65
70.56
71.01
71.12
71.15
71.23
71.34
75.67
83.77
112.20
113.84
114.44
114.56
123.29
123.83
133.56
148.22
152.79
159.53
166.43
Figure S20. 13C NMR spectrum (75 MHz, CDCl3, room temperature) of compound 14.
‐ S18 ‐
Figure S21. Electrospray ionization spectrum of compound 14.
2.8. Synthesis of monomer 2
Compound 14 (310 mg, 0.45 mmol), [Au(C^N^C)(Cl)] (210 mg, 0.46 mmol), CuI (20.0 mg,
0.10 mmol) and NEt3 (2 mL) in 30 mL CH2Cl2 were stirred at room temperature for 48 hours
under nitrogen atmosphere. After the reaction was complete, the solvent was evaporated under
reduced pressure and the residue was purified by flash column chromatograph
(CH2Cl2/CH3OH, 100 : 1 v/v as the eluent) to afford compound 2 as a yellow oil (420 mg,
84%). The 1H NMR spectrum of compound 2 is shown in Figure S22. 1H NMR (300 MHz,
CDCl3, room temperature) (ppm): 8.08 (d, J = 7.2 Hz, 2H), 7.84 (t, J = 8.0 Hz, 1H), 7.65 (m,
1H), 7.54 (t, J = 7.8 Hz, 5H), 7.45 (d, J = 8.0 Hz, 2H), 7.38 (t, J = 7.3 Hz, 2H), 7.23 (m, 2H),
6.87 (m, 3H), 4.28 (t, J = 6.7 Hz, 2H), 4.24–4.17 (m, 4H), 3.99 (m, 2H), 3.96–3.90 (m, 4H),
3.84–3.78 (m, 4H), 3.78–3.71 (m, 4H), 3.67 (m, 8H), 1.84–1.60 (m, 6H), 1.30 (s, 14H). The 13C NMR spectrum of compound 2 is shown in Figure S23. 13C NMR (75 MHz, CDCl3, room
temperature) δ (ppm): 166.9, 166.4, 164.7, 158.2, 152.8, 149.0, 148.2, 142.1, 136.5, 133.1,
131.8, 126.6, 125.2, 123.8, 123.3, 126.6, 125.2, 123.8, 123.3, 118.8, 116.8, 114.5, 114.3,
112.2, 100.5, 89.4, 71.3, 71.2, 71.1, 71.0, 70.6, 69.6, 69.5, 69.3, 69.1, 68.0, 65.0, 29.7, 29.6,
29.4, 29.3, 28.8, 26.1. ESI–MS m/z: [M + K]+, C56H66AuKNO10, 1148.5.
‐ S19 ‐
1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0
14.22
7.72
8.87
4.64
4.43
4.22
1.80
4.47
2.26
3.00
2.11
2.18
1.98
4.75
1.17
1.10
1.85
1.25
1.30
1.42
1.44
1.47
1.65
1.73
1.75
1.77
1.80
3.67
3.72
3.74
3.75
3.79
3.81
3.82
3.92
3.94
3.95
3.98
4.00
4.19
4.20
4.22
4.25
4.28
4.30
6.85
6.86
6.88
6.89
7.23
7.23
7.26
7.26
7.36
7.38
7.43
7.46
7.52
7.54
7.57
7.64
7.64
7.67
7.84
8.07
8.09
Figure S22. 1H NMR spectrum (300 MHz, CDCl3, room temperature) of monomer 2.
Figure S23. 13C NMR spectrum (75 MHz, CDCl3, room temperature) of monomer 2.
‐ S20 ‐
185.0 318.4467.2
605.5
1148.5
+MS, 0.0-0.2min (#1-#11)
0
1
2
3
6x10Intens.
200 400 600 800 1000 1200 1400 1600 1800 m/z
Figure S24. Electrospray ionization spectrum of monomer 2.
2.9. Synthesis of compound 15
A solution of 4-((10-bromodecyl)oxy)benzaldehyde (10.0 g, 29.3 mmol) and 1-butylamine
(6.42 g, 88.0 mmol) in MeOH (100 mL) was stirred at room temperature overnight. Then
NaBH4 (0.91 g) was added and stirred at room temperature for 6 hours. After the quench of
reaction by addition of water, the resulting solution was extracted with H2O/CH2Cl2. The
organic extracts was dried over anhydrous Na2SO4 and evaporated to afford a crude product.
The mixture of the crude product, di-tert-butyl dicarbonate (6.40 g, 29.3 mmol) and Et3N
(3.00 g, 29.6 mmol) in MeOH (100 mL) was stirred at room temperature overnight. The
solvent was removed and the residue was purified by flash column chromatography
(petroleum ether/CH2Cl2, 5 : 1 v/v as the eluent) to afford 15 as a colorless oil (9.27 g, 63%).
The 1H NMR spectrum of compound 15 is shown in Figure S25. 1H NMR (300 MHz, CDCl3,
room temperature) δ 7.13 (br, 2H), 6.82 (d, J = 8.6 Hz, 2H), 4.34 (s, 2H), 3.92 (t, J = 6.5 Hz,
2H), 3.39 (t, J = 6.9 Hz, 2H), 3.23–3.01 (br, 2H), 1.92–1.70 (m, 4H), 1.44 (m, 12H),
1.35–1.19 (m, 11H), 0.89 (m, 3H). The 13C NMR spectrum of compound 15 is shown in
Figure S26. 13C NMR (75 MHz, CDCl3, room temperature) δ (ppm): 158.3, 130.5, 129.0,
128.4, 79.4, 68.0, 49.7, 49.1, 46.0, 34.0, 32.8, 30.1, 29.7, 29.4, 29.3, 28.7, 28.5, 28.2, 26.0,
20.0, 13.9. ESI–MS m/z: [M + H]+, C26H45O3NBr, 498.25787.
‐ S21 ‐
Figure S25. 1H NMR spectrum (300 MHz, CDCl3, room temperature) of compound 15.
Figure S26. 13C NMR spectrum (75 MHz, CDCl3, room temperature) of compound 15.
‐ S22 ‐
Figure S27. Electrospray ionization spectrum of compound 15.
2.10. Synthesis of compound 16
Compound 15 (5.00 g, 10.0 mmol), 1,3,5-benzenetricarboxylic acid (0.53 g, 2.50 mmol)
and 1,1,3,3-tetramethylguanidine (0.87 g, 7.55 mmol) in 50 mL DMSO were stirred at room
temperature for 48 hours.[S7] After the reaction was complete, the solvent was extracted with
H2O/CH2Cl2. The organic extracts was dried over anhydrous Na2SO4 and evaporated with a
rotary evaporator. The residue was purified by flash column chromatograph (petroleum
ether/CH2Cl2, 2 : 1 v/v as the eluent) to afford compound 16 as a colorless oil (9.27 g, 63%).
The 1H NMR spectrum of compound 16 is shown in Figure S28. 1H NMR (300 MHz, CDCl3,
room temperature) δ 8.84 (s, 3H), 7.13 (br, 6H), 6.82 (d, J = 8.6 Hz, 6H), 4.36 (t, J = 6.7 Hz,
12H), 3.92 (t, J = 6.5 Hz, 6H), 3.09 (br, 6H), 1.78 (m, 12H), 1.46 (m, 42H), 1.38–1.21 (m,
33H), 0.88 (t, J = 7.3 Hz, 9H). The 13C NMR spectrum of compound 16 is shown in Figure
S29. 13C NMR (75 MHz, CDCl3, room temperature) δ (ppm): 165.1, 158.3, 134.4, 131.5,
‐ S23 ‐
130.5, 129.0, 128.4, 114.4, 79.3, 68.0, 65.8, 49.7, 45.8, 30.1, 29.7, 29.5, 29.4, 29.3, 28.7, 28.5,
26.1, 26.0, 20.0, 13.9. ESI–MS m/z: [M + H]+, C87H136O15N3, 1462.99634.
12.9
3
34.1
642
.70
13.0
7
5.94
6.00
11.9
8
6.13
6.14
3.00
0.85
0.88
0.90
1.22
1.25
1.29
1.33
1.37
1.46
1.74
1.77
1.79
1.82
3.09
3.90
3.92
3.94
4.34
4.36
4.39
6.81
6.84
7.12
7.14
7.26
8.84
Figure S28. 1H NMR spectrum (300 MHz, CDCl3, room temperature) of compound 16.
Figure S29. 13C NMR spectrum (75 MHz, CDCl3, room temperature) of compound 16.
‐ S24 ‐
Figure S30. Electrospray ionization spectrum of compound 16.
2.11. Synthesis of monomer 3
55
Compound 16 (2.00 g, 1.37 mmol) was dissolved in 10% HCl/ethyl acetate (100 mL) and
stirred overnight. After the reaction, the white solid was filtered, washed with ethyl acetate
thoroughly, and dissolved in water/acetone (200 ml). The saturated aqueous solution of
NH4PF6 was added and stirred at room temperature for 3 hours. Then acetone was evaporated
with a rotary evaporator to afford a white precipitate, which was filtered off and washed with
deionized water to afford monomer 3 as a white solid (1.45 g, 66%). Mp: 196.3−197.5 oC.
The 1H NMR spectrum of compound 3 is shown in Figure S31. 1H NMR (300 MHz, CD3CN,
room temperature) δ 8.66 (s, 3H), 7.28 (d, J = 8.6 Hz, 6H), 6.88 (d, J = 8.2 Hz, 6H), 4.29 (t, J
= 6.3 Hz, 6H), 3.99 (s, 6H), 3.91 (t, J = 6.6 Hz, 6H), 2.96–2.85 (m, 6H), 1.69 (m, 12H), 1.53
(m, 6H), 1.44–1.17 (m, 42H), 0.87 (t, J = 7.3 Hz, 9H). The 13C NMR spectrum of compound
3 is shown in Figure S32. 13C NMR (75 MHz, CD3CN, room temperature) δ (ppm): 164.3,
159.8, 133.3, 131.4, 131.3, 122.0, 114.4, 67.6, 65.4, 50.7, 47.0, 28.9, 28.7, 28.6, 28.0, 27.2,
‐ S25 ‐
25.4, 19.0, 12.4. [M + Na]+, C72H114O9N3NaP3, 1622.73828.
8.34
40.50
7.32
13.21
6.42
5.68
5.27
6.05
6.00
5.77
3.16
0.84
0.87
0.89
1.24
1.28
1.31
1.34
1.36
1.55
1.67
1.70
1.72
2.88
2.91
2.93
3.88
3.91
3.93
3.99
4.26
4.29
4.31
6.86
6.89
7.27
7.29
8.66
Figure S31. 1H NMR spectrum (300 MHz, CD3CN, room temperature) of compound 3.
Figure S32. 13C NMR spectrum (75 MHz, CD3CN, room temperature) of compound 3.
‐ S26 ‐
Figure S33. Electrospray ionization spectrum of compound 3.
‐ S27 ‐
3. UV/Vis titration between 6 and pyrene
400 450 500 550
0.0
0.2
0.4
0.6
Abs
orba
nce
Wavelength (nm)
Figure S34. UV/Vis absorption spectra change upon stepwise addition of pyrene to monomer 6 at 5.00 × 10-5 M in CHCl3/CH3CN (2/1, v/v). The weak binding affinity for 6/pyrene is manifested by the very slight absorption changes in UV/Vis spectra. Therefore, the bis-alkynylplatinum(ІІ) terpyridine molecular tweezer/pyrene recognition motif is not a suitable candidate for the fabrication of supramolecular hyperbranched polymers.
‐ S28 ‐
4. 1H NMR titration between 6 and 7 1H NMR titration experiments were performed between the monotopic compounds 6 and 7,
for which the initial concentration of compound 7 was kept constant at 5.00 mM while
concentration of compound 6 was systematically varied (Figure S35). Based on the molar
ratio plot (Figure 1a in the maintext), the complexation stoichiometry between compound 6
and compound 7 is determined to be 1 : 1 at room temperature.
[7]
[7]+0.28 eq.[6]
[7]+0.51 eq.[6]
[7]+0.71 eq.[6]
[7]+0.87 eq.[6]
[7]+1.00 eq.[6]
[7]+1.15 eq.[6]
[7]+1.26 eq.[6]
[7]+1.36 eq.[6]
[7]+1.53 eq.[6]
[7]+1.67 eq.[6]
[7]+1.78 eq.[6]
[7]+1.85 eq.[6]Ha Hb
HbHa
O6
NAu
HaHb
Br
Compound 7
HO N
2PF6
NN
NPt
NN
NPt
O6
2+ _
Compound 6
Figure S35. 1H NMR titration spectra (300 MHz, CDCl3/CD3CN (2/1, v/v), room temperature) of compound 7 at the concentration of 5.00 mM upon stepwise addition of compound 6.
‐ S29 ‐
5. UV/Vis titration experiments for complexes 6/2 and 1/2
Progressive addition of 2 to the tweezer-containing compounds such as 1 and 6 led to a
gradual decrease of the intensity for MLCT/LLCT absorption bands in UV/Vis spectra
(Figure S36–37). Hence, treatment of the collected absorbance data at 460 nm (A) vs the
concentration of guest added (CA) with a non-linear least-squares curve-fitting equation
affords the association constants. Specifically, for 1 : 1 host/guest complexation, binding
constants are calculated according to the following equation:[S8]
(Equation S1)
A0 and A are the absorbance of the host at a selected wavelength with and without presence
of the guest, respectively, [C0] is the total concentration of the host, [CA] is the concentration
of the guest, Alim is the limiting value of absorbance with the presence of excess guest and KS
is the binding constant.
400 450 500 550
0.0
0.4
0.8
1.2
Abs
orb
ance
Wavelength (nm)0.0000 0.0001 0.0002 0.0003
0.24
0.28
0.32
0.36
Ab
sorb
ance
at 4
60
nm
Guest (mol/L)
Figure S36. Left: UV/Vis absorption spectra change upon stepwise addition of 2 to 6 at 5.00 × 10-5 M in CHCl3/CH3CN (2/1, v/v); right: UV/Vis absorption spectra change at 460 nm. The red line was obtained from the non-linear curve-fitting. K6·2 = (1.43 ± 0.61) × 104 M–1.
400 450 500
0.0
0.4
0.8
Abs
orba
nce
Wavelength (nm)0.0000 0.0001 0.0002
0.28
0.32
0.36
0.40
Abs
orba
nce
at 4
60 n
m
Guest (mol/L)
Figure S37. Left: UV/Vis absorption spectra change upon stepwise addition of 2 to 1 at 5.00 × 10-5 M in CHCl3/CH3CN (2/1, v/v); right: UV/Vis absorption spectra change at 460 nm. The red line was obtained from the non-linear curve-fitting. K1·2 = (6.66 ± 1.11) × 103 M–1.
1/22lim 0
0 0 0 00
1/ 1/ 42 A S A S A
A AA A C C K C C K C C
C
‐ S30 ‐
6. Molecular recognition studies for the four monotopic compounds
uc
uc
uc
c
c
uc
uc
uc
uc
uc
cc uc
uc
uc
c
uc
uc
c
c
c
ucuc
uc uc
cc
c c
i)
h)
g)
f)
e)
d)
c)
b)
a)
HON
2PF6
NN
NPt
NN
NPt
O
2+
6
6
BrO5
NAu
7
O
O
O
OO
O
OO
O
B21C7 Ester
NH2
PF6
Secondary Ammonium Salt
Figure S38. 1H NMR spectra (300 MHz, CDCl3/CD3CN (2/1, v/v), room temperature) of a) 6, 7, B21C7 ester and secondary ammonium salt with 1 : 1 : 1 : 1 molar ratio; b) 6, B21C7 ester and secondary ammonium salt with 1 : 1 : 1 molar ratio; c) 7, B21C7 ester and secondary ammonium salt with 1 : 1 : 1 molar ratio; d) 6, 7 and B21C7 ester with 1 : 1 : 1 molar ratio; e) 6, 7 and secondary ammonium salt with 1 : 1 : 1 molar ratio; f) B21C7 ester; g) secondary ammonium salt; h) 7; i) 6. Peaks corresponding to complexed and uncomplexed units are designated as “c” and “uc”, respectively. Based on Figure S38d–e, preferential recognition between molecular tweezer/gold(III) alkynyl complexes is confirmed without the participation of B21C7 ester or secondary ammonium salt. Meanwhile, specific recognition between B21C7 ester and secondary ammonium salt motifs is also demonstrated, without the involvement of 6 or 7 (Figure S38b–c). Moreover, after mixing equivalent amounts of monotopic compounds together, the resulting spectra (Figure S38a) are almost the overlapping 1H NMR spectra of the corresponding 6/7 and B21C7/secondary ammonium salt complexes, definitely supporting the non-interfering complexation properties for the two non-covalent recognition motifs.
‐ S31 ‐
7. Complexation studies for 1–3 via step-wise self-assembly pathway
H22p
H22oH20p
H20oH18o+p
H23p
H23o
H24p
H24o H21oH21p
H19o+p
a)
b)
c)
d)
e)
H25
H25o
H25p
H23 H24
H17
H12
H14
H22
H13
H18
H20
H15H16 H19
H21
H18
H20H22 H19 H21
H1o
H3oH1p
H3p
Figure S39. 1H NMR spectra (300 MHz, CDCl3/CD3CN (2/1, v/v), room temperature) of a) 3; b) mixture of 1, 2 and 3 with 3 : 3 : 2 molar ratio; c) mixture of 1 and 2 with 1 : 1 molar ratio; d) 1; e) 2. [1] = [2] = 9 mM, [3] = 6 mM. Here “p” and “o” denote the polymeric and oligomeric species, respectively.
‐ S32 ‐
8. COSY NMR spectra for the mixture of 1–3
H24p
H24o
H23o
H23p
H2o+p
H1o+p
H4o+p
H3o+pH25o
H25pH5o+p
H21p
H21o
H22pH22o
H18o+p H19o+p
Figure S40. 1H-1H COSY NMR spectrum (400 MHz, CDCl3/CD3CN (2/1, v/v), room temperature) of the mixture of 1, 2 and 3 with 3 : 3 : 2 molar ratio (concentration of 1 is 9.0 mM). The spectrum facilitates the accurate proton assignments. Strong correlations could be seen between the protons H1 and the neighbouring proton H2 on the molecular tweezer unit. Moreover, the correlations between H18 and the neighbouring protons H19 on 2, H24 and H23 on 3 could also be observed. For the neighbouring B21C7 ester protons the correlations could also be visulized. Here “p” and “o” denote the polymeric and oligomeric species, respectively.
‐ S33 ‐
9. DOSY experiments for the linear and hyperbranched supramolecuar polymers
Figure S41. Two-dimensional diffusion-ordered NMR (DOSY) spectra of the supramolecular hyperbranched polymers (a and b) and the linear polymers (c and d) in CDCl3/CD3CN (2/1, v/v) at different monomer concentrations: (a) and (c), 70.0 mM; (b) and (d), 5.00 mM for 1. As the monomer concentration increases from 5.00 mM to 70.0 mM, the measured diffusion coefficients decrease dramatically from 3.75 × 10-10 to 5.12 × 10-12 m2 s-1. Similar trend is also observed for the linear supramolecular polymer, which declines from 5.83 × 10-10 to 8.49 × 10-11 m2 s-1 under the same conditions. When compared with the results, it is obvious that the self-assembling architectures exert significant impacts on the size of the resulting supramolecular assemblies.
d)c)
b)a)
‐ S34 ‐
10. Stimuli-responsive properties for 5
H24p
H24p
H24p
H24o
H24o
H24o
H25p
H25p
H25p
H25o
H25o
H25o
H23p
H23p
H23p
H23o
H23o
H23o
a)
b)
c)
Supramolecular 5
Supramolecular 5 + 1.0 eq. KPF6
Supramolecular 5 + 1.0 eq. KPF6 + 2.0 eq. 18-crown-6
Figure S42. Partial 1H NMR spectra (300 MHz, CDCl3/CD3CN (2/1, v/v), 298 K) of the supramolecular hyperbranched polymers 5 (8.0 mM based on monomer 1) with successive addition of KPF6 and 18-crown-6, respectively. Here “p” and “o” denote the polymeric and oligomeric species, respectively.
References:
[S1] H. K. Yip, L. K. Cheng, K. K. Cheung and C. M. Che, J. Chem. Soc. Dalton Trans., 1993, 2933.
[S2] Y. K. Tian and F. Wang, Macromol. Rapid Commun., 2014, 35, 337.
[S3] K.-H. Wong, K.-K. Cheung, M. C.-W. Chan and C.-M. Che, Organometallics, 1998, 17, 3505.
[S4] S. A. Hudson, K. J. McLean, S. Surade, Y.-Q. Yang, D. Leys, A. Ciulli, A. W. Munro, and C. Abell,
Angew. Chem., Int. Ed., 2012, 51, 9311.
[S5] G. T. Wang, C. Wang , Z. Q. Wang and X. Zhang, Langmuir, 2011, 27, 12375.
[S6] Y. K. Tian, Y. G. Shi, Z. S. Yang and F. Wang, Angew. Chem., Int. Ed., 2014, DOI:
10.1002/anie.201402192.
[S7] Q. B. Li, Y. Y. Bao, H. Wang, F. F. Du, Q. Li, B. K. Jin and R. K. Bai, Polym. Chem., 2013, 4, 2891.
[S8] Y. Tanaka, K. M. -C. Wong, V. W. -W. Yam, Chem. Eur. J., 2013, 19, 390.
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