• Bulletin of the Korean Chemical Society
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• v.26 no.3
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• pp.488-492
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• 2005

• Bulletin of the Korean Chemical Society
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• v.24 no.4
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• pp.484-488
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• 2003

Polycarbosilanes containing diacetylene and organosilacyclic groups, such as poly(1,1-diethynyl-1-silacyclopent-3-ene), poly(1,1-diethynyl-3-triethylsilyl-1-silacyclopent-3-ene), and poly(1,1-diethynyl-1- silacyclobutane), were synthesized by the Glaser oxidative coupling polymerization reactions of 1,1-diethynyl-1-silacyclopent-3-ene, 1,1-diethynyl-3-triethylsilyl-1-silacyclopent-3-ene, and 1,1-diethynyl-1-silacyclobutane, respectively. These materials are almost insoluble in usual organic solvents such as $CHCl_3$ and THF. The polymers were characterized by using several spectroscopic methods in solid state. FTIR spectra of all the polymeric materials show that the characteristic C≡C stretching frequencies appear at 2146-2170 $cm^{-1}$, in particular. The polymers in the solid state show that the strong maximum excitation peaks appear at 255-257 nm and the strong maximum fluorescence emission bands at 401-402 nm. About 71-87% of the initial polymer weights remain at 400 ℃ in nitrogen according to thermogravimetric analysis.

• Bulletin of the Korean Chemical Society
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• v.25 no.6
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• pp.889-894
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• 2004

Polyaddition reactions of 1,1-diethynyl-3-triethylsilyl-1-silacyclopent-3-ene with several organoborane derivatives have afforded the oligomeric materials containing organosilacyclic group and organoboron moiety along the oligomer main chains. All of these materials are soluble in THF as well as chloroform, and their molecular weights are in the range of 1,990/1,190-21,950/7,050 ($M_w/M_n$) with the polydispersity indexes of 1.67-3.43. The prepared oligomers are characterized by several spectroscopic methods such as $^1H,\;^{13}C, \;^{29}Si,\;^{11}B$ NMR and FTIR spectra along with elemental analysis. FTIR spectra of all the oligomers show that the new strong C=C stretching frequencies appear at 1599-1712 $cm^{-1}$, in particular. The UV-vis absorption spectra of the materials in THF solution exhibit the strong absorption bands at the ${\lambda}_{max}$ of 268-275 nm. The oligomeric materials show that the strong excitation peaks appear at the ${\lambda}_{max}$ of 255-279 nm and the strong fluorescence emission bands at the ${\lambda}_{max}$ of 306-370 nm. All the spectroscopic data suggest that the obtained materials contain both the organoboron ${\pi}$-conjugation moiety of C=C-B-C=C and the organosilacyclic group of 3-triethylsilyl-1-silacyclopent-3-ene along the oligomer main chains. The oligomers are thermally stable up to 162-200 $^{\circ}C$ under nitrogen.