Effect of Side Chain Rotaxane Structure on the Helix-Folding of Poly(M-Phenylene Diethynylene)
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Supporting Information for
Effect of Side Chain Rotaxane Structure on The Helix-Folding of Poly(m-phenylene diethynylene)
Sakiko Suzuki, Kazuki Matsuura, Kazuko Nakazono, and Toshikazu Takata*
Department of Organic and Polymeric Materials
Tokyo Institute of Technology
2-12-1 (H-126), Ookayama, Meguro-ku, Tokyo 152-8552, Japan
S1 Table of Contents
1. Materials and methods------S3
2. Experiments ------S4
3. Solubility of polyrotaxanes------S18
4. Spectra data of synthesized compounds
4-1. 1H NMR, 13C NMR and IR spectra------S19
4-2. UV-vis spectra------S28
5. References------S30
S2 1. Materials and Methods
All solvents were distilled or dried before use according to the general purification procedure.
Commercially available reagents were used without further purification unless otherwise noted. All
reactions were carried out under inert atmosphere of argon. SiO2 column chromatography was performed
using Wakogel C-400HG (Wako Pure Chemical Industries Ltd.). Al2O3 column chromatography was performed using Merck Aluminum Oxide 90 standardized. sec-Ammonium salt 1 and 4 were prepared according to the literature1.
High-resolution mass spectra (HR-MS) data were taken by the National University Corporation, Tokyo
Institute of Technology, Center for Advanced Materials Analysis, on request.
S3 2. Experiments
2-1. Synthesis of rotaxanes
Scheme S1
Synthesis of methylation of 3,5-dibromobenzoic acid S1 2
To a solution of 3,5-dibromobenzoic acid (4.0 g, 14 mmol) in methanol (120 mL) was added sulfuric acid
(0.12 mL, 2.1 mmol) in dropwise at r.t. After overnight reflux, the solution was concentrated under
reduced pressure. The residue was dissolved in CH2Cl2, and it was washed with water and brine, dried
over MgSO4, filtration and concentrated in vacuo. The residue was purified by recrystallized from methanol to give S1 (3.7 g, 12 mmol, 88%) as a white needle.
1 H NMR (CDCl3 298 K) δ 8.11 (d, J=1.7 Hz, 2H), 7.86 (t, J = 1.7 Hz, 1H), 3.93 (s, 3H) ppm.
1 Lit: H NMR (CDCl3, 300 MHz), δ 8.08 (s, 2H,), 7.82 (s, 1H), 3.91 (s, 3H) ppm.
Synthesis of methyl 3,5-di(trimethylsilylethynyl)benzoate S2 3
A suspension of S1 (3.7 g, 13 mmol), trimethylsilylacetylene (6.9 mL, 50 mmol), triphenylphosphine
(0.52 g, 2.0 mmol), CuI (0.38 g, 2.0 mmol), and PdCl2(PPh3)2 (0.50 g, 0.7 mmol) in dry triethylamine
(100 mL) was heated to 70 ºC and stirred overnight. After cooling to room temperature, the suspension was filtrated to remove the catalyst, and the filtrate was washed with diethylether. The combined filtrate
S4 was washed with 10% NH4Cl aq. The combined organic layer was dried over MgSO4 and concentrated under reduced pressure. The residue was purified by column chromatography (silicagel, n-hexane to dichloromethane:n-hexane 2:1) to give S2 (3.9 g, 12 mmol, 95%) as a pale brown solid.
1 H NMR (CDCl3, 298 K) δ 8.04, 8.04 (dd, J = 1.7 Hz, 1.7 Hz, 2H), 7.73,7.72, (tt, J = 1.6 Hz, 1.6 Hz, 1H),
3.91, 3.91 (ss, 3H), 0.24, 024 (ss, 18H) ppm.
1 Lit: H NMR (300 MHz, CDCl3) δ 8.0 (m, 2H), 7.7 (m, 1H), 3.9 (s, 3H), 0.2 (s, 18H) ppm.
Synthesis of 3,5-diethynylbenzoic acid S3 4
To a solution of S2 (3.9 g, 12 mmol) in dry THF (50 mL) was added a solution of KOH (3.4 g, 60 mmol)
in H2O (15 mL), and it was heated to 40 ºC overnight. After cooling to r.t., the solution was concentrated
under reduced pressure. The residue was added diethylether (70 mL) and H2O (50 mL), then neutralized with 1M HCl. Subsequently the aqueous mixture was extracted three times with diethylether (70 mL).
The combined organic layer was dried over MgSO4 and concentrated under reduced pressure. The titled
S3 (1.9 g, 11 mmol, 95%) was obtained as a pale brown solid, it was used without further purification to next step.
1 H NMR (CDCl3 298 K) δ 8.18 (d, J = 1.5 Hz, 2H), 7.81 (t, J = 1.5 Hz, 1H), 3.16 (s, 2H) ppm.
1 Lit: H NMR (250 MHz, CD3OD) δ 8.0 (d, 2H), 7.7 (t, 1H), 3.65 (s, 2H).
S5 Scheme S2
Synthesis of iodoethynylbenzene S4 5
To a solution of iodoform (4.1 g, 11 mmol), triphenylphosphine (2.9 g, 11 mmol) and tBuOK (1.1 g, 10 mmol) in THF 50 mL was added benzaldehyde (0.51 mL, 5.0 mmol) at r.t. After stirring for 15 min, the solution was cooled to -78 ºC. To reaction mixture was added the solution of tBuOK (2.8 g, 25 mmol) in
THF 10 mL and stirring for 15 min at -78 ºC. After additing of sat. NaCl aq.(75 mL) warming to r.t., the
aqueous mixture was extracted with diethylether. The combined organic layer was dried over MgSO 4 and concentrated under reduced pressure. The residue was purified by column chromatography (silicagel, n- hexane) to give S4 (0.95 g, 4.2 mmol, 83%) as pale yellow oil.
1 13 H NMR (400 MHz, CDCl3, 298 K) δ 7.43-7.39 (m, 2H), 7.31-7.29 (m, 3H) ppm; C NMR (100 MHz,
CDCl3, 298 K) δ 132.4, 128.9, 128.3, 123.4, 94.2, 6.6 ppm.
1 13 Lit: H NMR (400 MHz, CDCl3) δ 7.44-7.42 (m, 2H), 7.32-7.29 (m, 3H) ppm; C NMR (100 MHz,
CDCl3, 298K) δ 132.3, 128.8, 128.2, 123.4, 94.1, 6.1 ppm.
S6 Scheme S3
Synthesis of amino alcohol S5
Paraformaldehyde (0.30 g, 10 mmol) and formic acid 0.37 mL (10 mmol) were added to a solution of sec-
Ammonium-salt-containing benzyl alcohol1 (0.40 g, 1.0 mmol) in DMF (10 mL), and the suspension was subsequently heated to 50 °C for 15 h. The mixture was cooled to ambient temperature, diethylether was added to it, and the precipitate was removed by filteration. The organic layer was washed with washed
with NaHCO3 aq. (5 w%), H2O and brine, dried over MgSO4, and concentrated under reduced pressure. 5
(0.25 g, 0.93 mmol, 93%) was obtained as yellow clear oil.
1 H NMR (400 MHz, CDCl3 298K) δ 7.35 (d, J = 8.0 Hz, 2H), 7.31 (d, J = 8.0 Hz, 2H), 6.89 (s, 2H), 6.82
(s, 1H), 4.66 (s, 2H), 3.54 (s, 2H), 3.44 (s, 2H), 2.30 (s, 6H), 2.16 (s, 3H) ppm; 13C NMR (100 MHz,
CDCl3 298K) δ 139.9, 137.8, 137.7, 137.5, 129.4, 128.9, 127.0, 126.9, 64.9, 61.6, 61.4, 41.9, 21.2 ppm;
+ FAB-HR-MS calcd for C18H24NO [M+H] 270.1858, found 270.1851..
Synthesis of model monomer 5
The solution of S5 (0.30 g, 1.1 mmol), 3,5-diethynyl benzoic acid (0.50 g, 2.9 mmol), N,N′- diisopropylcarbodiimide (DIC, 0.32 mL, 2.2 mmol) and f tributylphosphane (0.060 mL, 0.22 mmol) in
CH2Cl2 (10 mL) was stirred overnight at room temperature. The mixture was poured into diethyl ether and the precipitates were removed by filteration. After the solvent was removed under reduced pressure, the residue was purified by The residue was purified by silicagel column chromatography (EtOAc/hexane
S7 = 1/4) to give 5 (0.27 g, 0.58 mmol, 58%) as pale yellow oil.
1 H NMR (400 MHz, CDCl3 298K) δ 8.13 (d, J = 1.5 Hz, 2H), 7.75 (t, J = 1.5 Hz, 2H), 7.40 (s, 4H), 6.97
(s, 2H), 6.88 (s, 1H), 5.35 (s, 2H), 3.53 (s, 2H), 3.46 (s, 2H), 3.13 (s, 2H), 2.31 (s, 6H), 2.18 (s, 3H) ppm;
13 C NMR (100 MHz, CDCl3 298K) δ 164.8, 139.7, 139.3, 1138.8, 137.6, 134.1, 133.2, 130.9, 129.2,
128.6, 128.4, 126.7, 122.9, 81.6, 78.9, 67.1, 61.8, 61.5, 42.2, 21.2 ppm; IR (NaCl) 3293 (ν C≡C-H, as), 2917
-1 (νC-H, as), 2836 (νC-H, as), 1724 (νC=O as), 1305 (νC(=O)-O-C, as), 1209 (νC–N, as), cm ; FAB-HR-MS calcd for
+ C29H28NO2 [M+H] 422.2120, found 422.2119.
Scheme S4
S8 Synthesis of Methyl 4-(aminomethyl)phenyl)benzoate hydrochloride S6 6
To a solution of 4-aminomethylbenzoic acid (3.0 g, 20 mmol) in methanol (70 mL) was added thionyl chloride (3.6 mL, 50 mmol) in dropwise at 0 ºC. After overnight stirring at r.t., the solution was concentrated under reduced pressure. The residue was washed with ethyl acetate and diethylether to give
S6 (3.7 g, 18 mmol, 92%) as a white solid.
1 H NMR (DMSO-d6, 298 K) δ 8.57 (br, 3H), 8.01 (d, J = 8.2 Hz, 2H), 7.65 (d, J = 8.2 Hz, 2H), 4.10 (s,
2H), 3.86 (s, 3H) ppm.
1 Lit: H NMR (300 MHz, DMSO-d6): δ 7.96 (d, J = 8.4, 2H), 7.60 (d, J = 8.4, 2H), 4.08 (s, 2H), 3.84 (s,
3H) ppm.
Synthesis of amide ester S7
To a solution of S3 (1.9 g, 12 mmol) and oxalyl chloride (2.0 mL, 24 mmol) in CHCl3 (20 mL) was added with a drop of DMF. After generation of gass was finished, the excess oxalyl chloride was distilled off by azeotropic distillation with toluene. The residue was dissolved in dry THF (20 mL) and added to a solution of S6 (2.2 g, 11 mmol) and triethylamine (4.6 mL, 33 mmol) in dry THF (20 mL) in dropwise at
0 ºC. After overnight stirring, 50 mL of water was added to the mixture and the aqueous mixture was
extracted three times with CH2Cl2 (20 mL), and combined organic layer was washed with water, 1M HCl,
brine, and sat. NaHCO3aq. Subsequently, it was dried over MgSO4 and concentrated under reduced pressure to give S7 (3.2 g, 10 mmol, 91%) as a pale brown solid.
1 m.p. 165.1-165.7 ºC; H NMR (CDCl3, 298 K) δ 8.00 (d, J = 8.1 Hz, 2H), 7.89 (d, J = 1.2 Hz, 2H), 7.71
13 (s, 1H), 7.39 (d, J = 8.1 Hz, 2H), 4.68, 4.67 (ss, 2H), 3.91 (s, 3H), 3.14 (s, 2H) ppm; C NMR (CDCl3,
S9 298 K) δ 166.8, 165.8, 143.0, 138.1, 134.7, 130.8, 130.0, 129.3, 127.5, 123.1, 81.5, 79.1, 52.1, 43.7 ppm;
IR (KBr) 3293 (νC≡C-H, as), 3234 (νN-H, at), 2953 (νC-H, st), 2906 (νC-H, st), 1706 (νC=O, st), 1641 (νC=O, st), 1530 (νN-H,
-1 + δ), 1287 (νC(=O)-O-C, st as), 1110 (νC-O-C, at as) cm ; FAB-HR-MS calcd for C20H16NO3 [M+H] 318.1130, found
318.1139.
Synthesis of ammonium salt S9
To a suspension of LiAlH4 (1.4 g, 36 mmol) in dry THF (70 mL) was added a solution of S7 (2.8 g, 9.0 mmol) in dry THF (30 mL) at 0 ºC. After overnight reflux, the reaction mixture was cooled to 0 ºC, and
sat. aq. sodium sulfate solution was slowly added to stop the H2 generation and the formed precipitate was
extracted with AcOEt. The filtrate was washed with water and brine, dried over MgSO4, and concentrated under reduced pressure to give S8 as a white solid. S8 was dissolved in MeOH (3 mL) and treated with conc. HCl (0.9 mL). After stirring at r.t. for 10 min, the mixture was poured into diethylether (100 mL), and the formed precipitates were collected by filtration. The precipitates were dissolved in MeOH (10
mL) again and an aqueous solution of NH4PF6 (1.7 g, 10 mmol) was added, and the methanol was distilled off under reduced pressure. The agueous suspension was filtered, and the precipitates were washed with water, then dried in vacuo to give S9 (2.2 g, 5.2 mmol, 75%) as a pink solid.
1 m.p. 167.9-169.0 ºC; H NMR (CD3CN, 298 K) δ 7.41 (s, 4H), 7.10 (s, 1H), 7.05 (s, 2H), 4.60 (s, 2H),
13 4.18 (s, 2H), 4.12 (s, 2H), 2.31 (s, 6H) ppm; C NMR (CD3CN, 298 K) δ 145.5, 137.6, 136.7, 133.1,
131.7, 130.3, 128.7, 124.8, 82.8, 81.5, 64.6, 53.0, 51.9 ppm; IR (KBr) 3405 (νC≡C-H, as), 836 (νP-F, as), 559
–1 + (νP-F, s) cm ; FAB-HR-MS calcd for C19H18NO [M-PF6] 276.1388, found 276.1384.
S10 Synthesis of sec -ammonium salt-type rotaxane S10
According to procedure of 2, S9 (0.8 g, 2.0 mmol), dibenzo-24-crown-8 ether (1.0 g, 2.4 mmol), 3,5- dimethylbenzoic acid (0.50 g, 3.0 mmol), tributylphosphane (0.10 mL, 0.40 mmol), and N,N’- diisopropylcarbodiimide (DIC, 0.59 mL, 4.0 mmol) were used. The reaction mixture was poured into diethylether (100 mL). The collected precipitates were purified by recrystallization from chloroform and
2-propanol to give S10 (1.8 g, 1.8 mmol, 88%) as a white solid.
1 m.p. 175.1-180.2 ºC; H NMR (CDCl3 298 K) δ 7.67 (s, 2H), 7.45 (s, 2H), 7.35 (d, J = 8.0 Hz, 2H), 7.33
(s, 1H), 7.29 (d, J = 8.0 Hz, 2H), 7.20 (s, 2H), 6.88-6.76 (m, 8H), 5.30 (s, 2H), 4.66-4.63 (m, 2H), 4.48-
4.45 (m, 2H), 4.10-4.09 (m, 8H), 3.79-3.77 (m, 8H), 3.52-3.44 (m, 4H), 3.11 (s, 2H), 2.36 (s, 6H), ppm;
13 C NMR (CDCl3 298 K) δ 166.4, 147.0, 138.0, 137.7, 135.3, 134.8, 132.9, 132.6, 130.9, 129.7, 129.2,
128.2, 127.2, 122.7, 121.7, 112.7, 81.5, 79.2, 70.6, 70.1, 68.0, 65.6, 52.3, 51.4, 21.0 ppm; IR (KBr) 3290
(νC≡C-H, as), 2917 (νC-H, as), 2879 (νC-H, as), 1717 (νC=O as), 1506 (νC=C, as), 1214 (νC(=O)-O-C,as), 1057 (νC-O-C, as), 874
-1 + (νP-F, as), 557 (νP-F, s) cm ; FAB-HR-MS calcd for C52H58NO10 [M-PF6] 850.4055, found 850.4053.
Synthesis of tert- amine-type rotaxane 6
According to the above procedure of 3, sec-ammonium type rotaxane S10 (1.0 g, 1.0 mmol), paraformaldehyde (0.30 g, 10 mmol) and sodium triacetoxyborohydride (1.1 g, 5.0 mmol) were used.
The reaction mixture was purified by short column chromatography (aluminium oxide, EtOAc) and recrystallized from chloroform and 2-propanol. 6 (0.63 g, 0.72 mmol, 72%) was obtained as a pale brown solid.
1 m.p. 162.3-163.2 ºC; H NMR (CDCl3 298 K) δ 8.18 (d, J = 7.6 Hz, 2H), 8.15 (s, 2H), 7.50 (s, 1H), 7.44
(s, 2H), 7.15 (d, J = 7.6 Hz, 2H), 7.09 (s, 2H), 6.91-6.85 (m, 9H), 6.04 (s, 2H), 4.13-4.06 (m, 8H), 3.75-
S11 3.66 (m, 8H), 3.44 (s, 2H), 3.29 (s, 2H), 3.27-3.25 (m, 4H), 3.08 (s, 2H), 2.94-2.91 (m, 8H), 2.22 (s, 6H),
13 2.11 (s, 3H) ppm; C NMR (CDCl3 298 K) δ 167.0, 148.4, 140.6, 137.4, 136.6, 135.7, 133.9, 133.9,
132.6, 130.7, 128.5, 128.1, 127.9, 122.1, 120.3, 111.4, 82.7, 77.6, 69.4, 69.1, 67.8, 66.8, 62.2, 59.9, 42.1,
20.7 ppm; IR (KBr) 3293 (νC≡C-H, as), 3264 (νC≡C-H, as), 2913 (νC-H, as), 2876 (νC-H, as), 1712 (νC=O as), 1505 (νC=C,
-1 + as), 1218(νC(=O)-O-C, as), 1055 (νC-O-C, as), cm ; ESI-TOF HR-MS calcd for C52H58NO10 [M+H] 870.4217, found 870.4194.
Synthesis of tert -ammonium salt-type rotaxane 6•TFA.
According to the above procedure of 3•TFA, rotaxane 5 (50 mg, 57 μmol) was used. This reaction gave
6•TFA (50 mg, 51 mmol, 89%) as a white solid.
1 m.p. 120.5-125.5 ºC; H NMR (CDCl3 298 K) δ 7.86 (s, 2H), 7,76 (br, 1H), 7.67 (s, 2H), 7.43 (d, J = 8.3
Hz, 2H), 7.29 (d, J = 8.3 Hz, 2H), 7.21 (s, 1H), 7.21 (s, 1H), 6.90-6.76 (m, 8H), 5.31, 5.31 (ss, 2H), 5.23-
5.20 (m, 1H), 4.85-4.82 (m, 1H), 4.53-4.47 (m, 1H), 4.29-4.25 (m, 1H), 4.19-4.04 (m, 8H), 3.86-3.74 (m,
13 8H), 3.67-3.51 (m, 8H), 3.06 (s, 2H), 2.94, 2.92 (ss, 3H), 2.35 (s, 6H) ppm; C NMR (CDCl3 298 K) δ
166.5, 147.1, 147.0, 138.1, 137.9, 136.0, 134.9, 132.5, 131.6, 129.7, 128.7, 128.2, 127.3, 121.9, 121.3,
121.1, 112.1, 111.6, 82.3, 78.5, 71.6, 71.4, 70.4, 70.2, 68.0, 67.8, 65.7, 60.3, 59.2, 39.1, 21.1 ppm; IR
(KBr) 3288 (νC≡C-H, as), 2919 (νC-H, as), 2879 (νC-H, as), 1715 (νC=O as), 1695 (νC=O as), 1505 (νC=C, as), 1212 (νC(=O)-
-1 + O-C, as), 1055 (νC-O-C, as), cm ; ESI-TOF HR-MS calcd for C53H60NO10 [M-CF3COO] 870.4212, found
870.4213.
S12 Scheme S5
Synthesis of S-( R )-11
According to procedure of 2, S9 (0.31 g, 0.74 mmol), (R)-binaphthobenzo-26-crown-8-ether (0.50 g, 0.74 mmol), 3,5-di-tert-butylbenzoic acid (0.22 g, 0.96 mmol), tributylphosphane (45 μL, 0.20 mmol), and
N,N’-diisopropylcarbodiimide (DIC, 0.30 mL, 2.0 mmol) were used. The reaction mixture was poured
into diethylether (100 mL). The collected precipitates were purified by recycle preperative GPC (CHCl3) to give S-(R)-11 (0.55 g, 0.44 mmol, 59%) as foam.
1 [α]D25: +139° (c = 0.10, THF); m.p. 147.2 – 149.0 °C; H NMR (CDCl3 298 K) δ 7.94 (s, 2H), 7.91-7.85
(m, 4H), 7.62 (s, 1H), 7.46-7.10 (m, 13H), 6.87-6.67 (m, 6H), 5.34 (s, 2H), 4.34-3.90 (m, 10H), 3.78-3.70
13 (m, 6H), 3.60-3.53 (m, 4H), 3.39-2.94 (m, 12H), 3.09 (s, 2H), 1.34 (s, 18H) ppm; C NMR (CDCl3 298
K) δ 166.9, 154.2, 154.1, 151.2, 146.7, 146.7, 138.2, 135.7, 133.7, 133.6, 133.1, 132.1, 130.4, 130.3,
130.2, 130.1, 129.9, 129.6, 129.3, 128.3, 128.3, 128.2, 127.4, 126.7, 125.1, 124.9, 124.6, 124.4, 123.8,
122.9, 122.1 122.0, 121.6, 120.8, 117.2, 116.5, 112.8, 81.4, 79.4, 71.0, 70.9, 70.9, 70.7, 70.6, 70.5, 70.4,
70.3, 69.7, 69.5, 68.6, 68.3, 65.7, 52.2, 51.4, 34.9, 31.3 ppm; IR (KBr) 3274 (νC≡C-H, as), 3264 (νC≡C-H, as),
2956 (νC-H, as), 2872 (νC-H, as), 1728 (νC=O as), 1502 (νC=C, as), 1217 (νC(=O)-O-C, as), 1106 (νC-O-C, as), 846 (νP-F, as),
-1 + 558 (νP-F, s) cm ; FAB-HR-MS calcd for C72H78NO10 [M-PF6] 1116.5620, found 1116.5625.
S13 Synthesis of tert- amine-type rotaxane ( R )-7
According to the above procedure of 3, sec-ammonium type rotaxane S11 (0.24 g, 0.18 mmol), paraformaldehyde (60 mg, 2.0 mmol) and sodium triacetoxyborohydride (0.23 g, 1.1 mmol) were used.
The reaction mixture was purified by column chromatography (aluminium oxide, EtOAc/hexane = 4/1).
(R)-7 (0.12 g, 0.11 mmol, 58%) was obtained as a pale brown solid.
1 [α]D25: +168° (c = 0.10, THF); m.p. = 110.3-112.1 °C; H NMR (CDCl3 298 K) δ 7.92 (s, 2H), 7.88 (d, J =
9.8 Hz, 1H), 7.78 (d, J = 9.8 Hz, 1H), 7.75 (d, J = 8.3 Hz, 1H), 7.58 (s, 1H), 7.48 (s, 1H), 7.40 (s, 2H),
7.34-7.16 (m, 11H), 6.91 (d, J = 7.8 Hz, 2H), 6.80-6.64 (m, 4H), 5.38 (s, 2H), 4.30-4.27 (m, 1H), 4.06-
4.04 (m, 1H), 3.95-3.88 (m, 3H), 3.75-3.73 (m, 1H), 3.67-3.64 (m, 2H), 3.57-3.55 (m, 2H), 3.46-3.44 (m,
13 2H), 3.27-2.78 (m, 16H), 3.03 (s, 2H), 2.05 (s, 3H), 1.29 (s, 18H) ppm; C NMR (CDCl3 298 K) 167.4,
154.2, 154.0, 150.6, 148.2, 148.1, 140.5, 136.7, 135.0, 134.0, 133.9, 133.8, 132.7, 130.3, 129.5, 129.3,
129.1, 129.1, 129.0, 128.6, 127.9, 127.8, 126.5, 125.9,125.7, 125.4, 125.2, 124.1, 123.2, 123.1, 122.1,
120.3, 119.3, 119.0, 114.6, 111.5, 111.4, 82.8, 77.6, 69.6, 69.3, 69.2, 69.1, 67.9, 67.4, 67.4, 67.0, 66.7,
62.0, 60.4, 42.1, 34.8, 31.3 ppm; IR (KBr) 3230 (νC≡C-H, as), 2948 (νC-H, as), 2869 (νC-H, as), 1724 (νC=O as), 1504
-1 + (νC=C, as), 1230 (νC(=O)-O-C, as), 1068 (νC-O-C, as) cm ; FAB-HR-MS calcd for C73H80NO10 [M+H] 1130.5777, found 1130.5786.
2-2 Polymerization of rotaxanes
Typical polymerization of rotaxane monomer 7
In a schlenk tube, a solution of rotaxane monomer (0.20 mmol) and CuCl(I) (6.0 mg, 60 μmol) in
pyridine (1.0 mL) was heated to 30 ºC with bubbling oxygen. After stirring for 3 h, 10 mL of CHCl3 and
10% NH4Cl aq. were added to the mixture and stirred overnight. The combined organic layer was washed
S14 with water and brine, dried over MgSO4, and concentrated under reduced pressure. The residue was
dissolved in CHCl3 (5.0 mL) and poured into n-hexane (50 mL), followed by the formed precipitates were collected by filtration.
Scheme S6
Polymerization of rotaxane 2
2 (0.2 g, 0.2 mmol) and CuCl(I) (6.0 mg, 60 μmol) were used and stirred for 3 h. However the polymerization did not proceeded. When the reaction mixture was heated to 60 ºC, gel product was obtained.
Scheme S7
Polymerization of rotaxane 3•TFA
3•TFA (0.2 g, 0.2 mmol) and CuCl(I) (6.0 mg, 60 μmol) were used and stirred for 3 h. however the
S15 polymerization did not proceeded, and the oligomer and monomer were recovered.
2-3. Acidofication and Neutralization of polyrotaxanes
Scheme S8
Neutralization of poly-3•TFA
A solution of poly-3•TFA (15 mg, 15 μmol) in CH2Cl2 (10 mL) was washed with 10% aqueous Na2CO3
(10 mL x 3), then dried over MgSO4 and concentrated in vacuo to afford poly-3 (8.2 mg, 9.4 μmol, 63%) as a white foam. The 1H NMR spectrum of product was in good agreement with poly-3.
Acidification of poly-6.
In accordance with the previously described procedure for the preparation of poly-6•TFA, poly-6 (50 mg, 60 μmol) and trifluoroacetic acid (0.050 mL, 1.2 mmol) were used. Poly 6•TFA (44 mg, 40 μmol,
78%) was obtained as a white solid.
1 H NMR (CDCl3, 298 K) δ 7.89 (s, 2H), 7.67 (s, 2H), 7.48 (d, J = 7.6 Hz, 2H), 7.44 (s, 1H), 7.40 (d, J =
7.6 Hz), 7.19 (s, 1H), 6.90–6.80 (m, 8H), 5.28 (s, 2H), 5.23–5.20 (m, 1H), 4.98–4.96 (m, 1H), 4.53 (br,
1H), 4.33 (br, 1H), 4.18–4.12 (m, 8H), 3.86–3.58 (m, 16H), 2.95 (s, 3H), 2.34 (s, 6H) ppm; IR (KBr)
− 2922 (νC-H, as), 2882 (νC-H, as), 1716 (νC=O as), 1690 (νCOO ), 1505 (νC=C, as), 1210 (νC(=O)-O-C, as), 1057 (νC-O-C, as),
−1 771 (νC-F) cm .
S16 Neutralization of poly-6•TFA
A solution of poly-6•TFA (15 mg, 15 μmol) in CH2Cl2 (10 mL) was washed with 10% aqueous Na2CO3
(10 mL x 3), then dried over MgSO4 and concentrated in vacuo to afford poly-6 (10 mg, 9.9 μmol, 66%) as a white foam. The 1H NMR spectrum of product was in good agreement with poly-6.
Scheme S9
Acidification of poly-( R )-7.
In accordance with the previously described procedure for the preparation of poly-(R)-7•TFA, poly-(R)-7
(50 mg, 44 μmol) and trifluoroacetic acid (0.050 mL, 1.2 mmol) were used. Poly-(R)-7•TFA (42 mg, 33
μmol, 75%) was obtained as a white solid.
1 [α]D25: +189° (c = 0.10, THF); H NMR spectrum of Poly-(R)-7•TFA was too broad to be analyzed, IR
(KBr) 2920 (νC-H, as), 2873 (νC-H, as), 1724 (νC=O as), 1512 (νC=C, as), 1201 (νC(=O)-O-C, as), 1133 (νC-O-C, as), 745 (νC-
-1 F, as)cm
S17 3. Solubility of polymers
Table S1. Solubility of polyrotaxanes
toluene CHCl3 THF CH2Cl2 CH3CN DMF DMSO MeOH H2O
poly-3 ± + + + – + – – – poly-3･TFA – ± – + + + +– ± –
poly-6 + + + + – + – – – poly-6･TFA ± + + + + + + + –
2 mg/ 0.5 mL;
+ : soluble, +– : soluble on heating, ±: partially soluble on heating, – : insoluble
S18 4. Spectra data of synthesized compounds 4-1. 1H NMR, 13C NMR and IR spectra
1 Fig. S1. H NMR spectrum of 3 (400 MHz, CDCl3, 298 K)
13 Fig. S2. C NMR spectrum of 3 (100 MHz, CDCl3, 298 K)
S19 Fig. S3. IR spectrum of 3 (KBr)
1 Fig. S4. H NMR spectrum of 3•TFA (400 MHz, CDCl3, 298 K)
13 Fig. S5. C NMR spectrum of 3•TFA (100 MHz, CDCl3, 298 K)
S20 Fig. S6. IR spectrum of 3•TFA (KBr)
1 Fig. S7. H NMR spectrum of poly-3 (400 MHz, CDCl3, 298 K)
S21 13 Fig. S8. C NMR spectrum of poly-3 (100 MHz, CDCl3, 298 K)
Fig. S9. IR spectrum of 3 and poly-3 (KBr)
S22 1 Fig. S10. H NMR spectra of poly-3•TFA (a) in CD3CN, (b) in CD3CN/D2O = 1/1 (400 MHz, 298 K).
Fig. S11. IR spectrum of Poly 3•TFA (KBr)
S23 1 Fig. S12. H NMR spectrum of 4 (400 MHz, CDCl3, 298 K)
S24 13 Fig. S13. C NMR spectrum of 4 (100 MHz, CDCl3, 298 K) Fig. S14. IR spectrum of 4 (KBr)
1 Fig. S15. H NMR spectrum of 6 (400 MHz, CDCl3, 298 K)
13 Fig. S16. C NMR spectrum of 6 (100 MHz, CDCl3, 298 K)
S25 Fig. S17. IR spectrum of 6 (KBr)
1 Fig. S18. H NMR spectrum of 6•TFA (400 MHz, CDCl3, 298 K)
13 Fig. S19. C NMR spectrum of 6•TFA (100 MHz, CDCl3, 298 K)
S26 Fig. S20. IR spectrum of 6•TFA (KBr)
1 Fig. S21. H NMR spectrum of poly-6 (400 MHz, CDCl3, 298 K)
13 Fig. S22. C NMR spectrum of poly-6 (100 MHz, CDCl3, 298 K)
S27 Fig. S23. IR spectra of 6 and poly 6 (KBr)
1 Fig. S24. H NMR spectrum of poly-6•TFA (400 MHz, CDCl3, 298 K)
S28 Fig. S25. IR spectrum of poly-6•TFA (KBr)
S29 4-2. UV-vis spectra
Fig. S26 UV—vis spectra of 3 (a: green line in CH2Cl2; yellow line in CH2Cl2/ CH3CN = 2/3); poly-3 (a:
blue line in CH2Cl2; red line in CH2Cl2/ CH3CN = 2/3); 3･TFA (a: green line in CH2Cl2; yellow line in
CH2Cl2/ CH3CN = 2/3); poly-3･TFA (a: blue line in CH2Cl2; red line in CH2Cl2/ CH3CN = 2/3)
(0.05 mM, 293 K).
( a ) poly-6 i n C H 2C l 2 ( b ) poly-6･TFA i n C H 2C l 2 2 2 poly-6 w i t h C H 3C N poly-6･TFA w i t h C H 3C N s s b b A A 1 1
6 i n C H 2C l 2 6･TFA i n C H 2C l 2
6 w i t h C H 3C N 6･TFA w i t h C H 3C N 0 0 250 300 350 400 250 300 350 400 W a v e le n g th [n m ] W a v e le n g th [n m ]
Fig. S27 UV-vis spectra of 6 (a: green line in CH2Cl2; yellow line in CH2Cl2/ CH3CN = 2/3); poly-6 (a:
blue line in CH2Cl2; red line in CH2Cl2/ CH3CN = 2/3); 6･TFA (a: green line in CH2Cl2; yellow line in
CH2Cl2/ CH3CN = 2/3); poly-6･TFA (a: blue line in CH2Cl2; red line in CH2Cl2/ CH3CN = 2/3)
(0.05 mM, 293 K).
S30 Fig. S28. Variable temperature UV-vis spectra of poly-3 (–10 ºC−60 ºC) (a) in a mixed solvent (CH2Cl2/
CH3CN = 2/3 (v/v)) (b) in a mixed solvent (CH2Cl2/ CH3CN = 1/4 (v/v)).
Fig. S29. UV-vis specta of poly-3 (solid line in CH2Cl2; dash line in CH2Cl2/ CH3CN = 2/3)
(0.005 mM, 293 K)
S31 5. References
S32 1 H. Kawasaki, N. Kihara and T. Takata, Chem. Lett. 1999, 10, 1015. 2 Q. D. Ling, E. T. Kang, K. G. Neoh, Macromolecules, 2003, 36, 6995. 3 B. Forster, J. Bertran and F. Teixidor, J. Organomet. Chem. 1999, 587, 67. 4 O. Torres, D. Yuksel, M. Bernardina, K. Kumar and D. Bong, ChemBioChem, 2008, 9, 1701. 5 J. Yan, J. Li and D. Cheng, Synlett, 2007, 2442. 6 X. Zhang, Z. Zhou, H. Yang, J. Chen, Y. Feng, L. Du, Y. Leng and J. Shen, Bioorg. Med. Chem. Lett. 2009, 19, 4455. 7 (a) A. S. Hay, J. Org. Chem. 1960, 25, 1275; (b) A. S. Hay, J. Org. Chem. 1962, 27, 3320. (c) T. Michinobu, H. Osako and K. Shigehara, Macromol. Rapid Commun. 2008, 29, 11.