| Budget Amount *help |
¥6,200,000 (Direct Cost: ¥6,200,000)
Fiscal Year 1993: ¥1,700,000 (Direct Cost: ¥1,700,000)
Fiscal Year 1992: ¥4,500,000 (Direct Cost: ¥4,500,000)
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| Research Abstract |
The new results obtained in this study are summarized as the following three aspects.
1. Thiophene-Silole Cooligomers and Copolymers : Correlation between Structure and Some Properties.
Thiophene-silole (silacyclopentadiene) copolymers, consisting of electron-excessive thiophene rings and electron-deficient silole rings, have been designed and the cooligomers and copolymers having thiophene-silole-thiophene skeleton (thiophene/silole ratio ; 2/1) as a monomer unit have been synthesized. The obtained new pi-conjugated systems exhibited unique optical properties, such as enormous bathochromic shifts in UV-visible absorption. Other thiophene-silole copolymers with thiophene/silole ratio 3/1 and 4/1 have also been prepared to evaluate the correlation between structures of polymer main chain and some properties. It has been found that an increase in the silole ratio in main chain leads bathochromic shifts in UV-visible region and an increase in the thiophene ratio leads high conductivities up
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to 2.4 S cm^<-1> with iodine-doping.
2. Synthesis and Properties of Thiophene-Cyclopentadienone Cooligomers.
Thiophene-cyclopentadienone cooligomers, consisting of electron-excessive thiophene rings and electron-deficient cyclopentadienone rings, have been synthesized as a model of the copolymers based on nickel(0)-promoted intramolecular cyclization of diyne derivatives and isocyanides. The cooligomers displayd considerable long-wave absorptions and exceptionally small bandgaps.
3. Novel Synthesis of 2, 5-Difunctional Siloles.
On the basis of a conceptually new endo-endo mode reductive intramolecular cyclization of diethynylsilanes has been first developed the new general synthetic route to 2, 5-difunctional siloles, such as 2, 5-dilithio-, dibromo-, and distannnylsilole, which are essential to synthesis of silole-containing novel pi-conjugated polymers. Moreover, 2, 2'-bisilole consisting of two silole rings, which have some interesting features in the structure and the electronic structure, has also been prepared as a model of promising target polymers, polysiloles. Less
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