Supporting information
Synthesis of a New Poly(dinaphthylacetylene) and Evaluation of Its Solution Conformation
Yuki Arakawa ・ Hidemine Furuya ・ Gen-ichi Konishi
1H-NMR and 13C-NMR spectra of 2-(2-Ethylhexyloxy)-6-[2-(6-methoxynaphthyl-2-y-
l)ethynyl]naphthalene (5) and 1H-NMR of poly(2-(2-Ethylhexyloxy)-6-[2-(6-methoxy-
naphthyl-2-yl)ethynyl]naphthalene) (a) are shown in Figure S1, S2 and S3.
Fig.S11H NMR spectrum of 5 (CDCl3,400 MHz).
Fig.S213C NMR spectrum of 5 (CDCl3,400 MHz).
Fig.S31H NMR spectrum of a(CDCl3,400 MHz).
Synthesis of diphenylacetylenes
We performed syntheses diphenylacetylenes according to Scheme S1.
Scheme S1 Synthesis of diphenyl diacetylenes.
1-phenyl-2-(p-tert-butyl)phenylacetylene (6)
p-tert-Butylphenylacetylene (2.1 ml, 12 mmol), iodobenzene (1.1 ml, 10 mmol), N-ethyldiis-opropylammine (2.1ml) and THF (20ml) was bubbling by argon. Pd(PPh3)4 (0.58 g, 0.5 mmol) and CuI (0.095 g, 0.5 mmoml) was added to the mixture solution. The mixture was stirring at 40 °C for 7 h and filtrated. The filtrate was washed 2M HCl (140 ml) and water, then, dried by anhydrous magnesium sulfate for 3 h. THF was evaporated and the crude product was purified by column chromatography on silica gel (eluent: hexane). Yield: 46%.1H NMR (CDCl3,400 MHz) δ 7.52-7.33 (m, 9H), 1.33 (s, 9H) ppm.
1-phenyl-2-(p-hexyl)phenylacetylene (7)
According to the general procedure for Sonogashira coupling, 1-etynyl-4-hexylbenzene (3.4 ml, 16 mmol), iodobenzene (2.23 ml, 20 mmol) and N-ethyldiisopropylammine (19.3 ml) was bubbling by argon. Pd(PPh3)4 (0.9 g,) and CuI (0.15 g,). Yield: 72%.1H NMR (CDCl3,400 MHz) δ7.54-7.52(m, 2H), 7.45 (d, 2H, J = 7.9 Hz), 7.34 (m, 3H), 7.16 (d, 2H, J = 7.9 Hz), 2.62 (t, 2H, J = 7.7 Hz), 1.65-1.58 (m, 2H), 1.39-1.26 (m, 6H), 0.89 (t, 3H, J = 6.80 Hz) ppm.
1-(p-hexyl)phenyl-2-(p-tert-butyl)phenylacetylene (8)
According to the general procedure for Sonogashira coupling, 1-etynyl-4-hexylbenzene (2.2 ml, 11 mmol), p-bromo-t-butylbenzene (2.3 ml, 13 mmol) and N-ethyldiisopropylammine (20 ml) was bubbling by argon. Pd(PPh3)4 (0.64 g,) and CuI (0.10 g,). Yield: 95%. 1H NMR (CDCl3,400 MHz) δ 7.44 (d, 2H, J = 8.0 Hz), 7.43 (d, 2H, 8.5 Hz), 7.35 (d, 2H, J = 8.5 Hz), 7.14 (d, 2H, J = 8.0 Hz), 2.57 (t, 2H, J = 7.7 Hz),1.65-1.56 (m, 2H), 1.36-1.26 (m, 15H), 1.65-1.56 (m, 2H), 0.88 (t, 3H, J = 6.4 Hz) ppm.,13C NMR (CDCl3,100 MHz)δ: 151.3, 143.2, 131.5, 131.3, 128.4, 125.3, 120.6, 120.5, 88.9, 88.8, 35.9, 34.7, 31.7, 31.2, 31.2, 28.9, 22.6, 14.1 ppm., HRMS (FAB) M+ Calcd for C24H30 : 318.2348, Found : 318.2345.
Fig. S41H NMR spectrum of 8(CDCl3,400 MHz).
Fig.S513C NMR of 8(CDCl3,100 MHz).
Polymerization
Synthesis of poly(diphenylacetylenes) (b-d), poly(phenylacetylenes) (e-h), poly(silylacetylenes) (i-m) and poly(tert-butylacetylene) (n) were carried out according to the each literature method. The typical procedure for polymerization is following: the monomer solution was prepared in a Schlenk tube equipped with a three-way stopcock while another Schlenk tube was charged with the main catalyst, a cocatalyst, and the solvent. The catalyst solution was aged at 80 °C (for tantalum and W catalysts) for 10 min. In the case of Rh catalysts, the catalyst solution was used directly. The monomer solution was added to the catalyst solution and polymerization was carried out for a given time at a given temperature. The polymer was precipitated in a large volume of methanol, filtered, and dried in vacuo overnight.
Polymerization of diphenylacetylenes
Scheme S2Polymerization of diphenylacetylenes.
Fig.S61H NMR spectrum ofd(CDCl3,400 MHz).
Polymerization of phenylacetylenes
Scheme S3 Polymerization of phenylacetylenes.
Fig. S71H NMR spectrum of e(CDCl3,400 MHz).
Fig. S81H NMR spectrum of g(CDCl3,400 MHz).
Polymerization of silylacetylenes
Scheme S4 Polymerization of silylacetylenes.
Polymerization oftert-Butylacetylene
Scheme S5 Polymerization of tert-Butylacetylene.
1