| Budget Amount *help |
¥19,110,000 (Direct Cost: ¥14,700,000、Indirect Cost: ¥4,410,000)
Fiscal Year 2013: ¥5,850,000 (Direct Cost: ¥4,500,000、Indirect Cost: ¥1,350,000)
Fiscal Year 2012: ¥5,850,000 (Direct Cost: ¥4,500,000、Indirect Cost: ¥1,350,000)
Fiscal Year 2011: ¥7,410,000 (Direct Cost: ¥5,700,000、Indirect Cost: ¥1,710,000)
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| Research Abstract |
We have developed highly efficient palladium catalysts for direct arylation polymerization (DArP) of aryl halides and heteroarenes to afford pi-conjugated polymers, which have found wide application in optoelectronic devices such as photovoltaic cells and field-effect transistors. The catalytic mechanism has been explored by kinetic experiments and DFT calculations using a presumed intermediate of the formula [PdAr(OAc)L]. This complex has a large propensity to be aggregated into a dimer or tetramer, which is inert to direct arylation. It has been found that the use of P(o-MeOC6H4)3 (L1) as L effectively control the aggregation, thereby leading to highly active catalysis. Thus, in the presence of catalytic amounts of palladium precursor and L1 (1 mol%), several kinds of dibromoarenes are successfully coupled with 2,3,5,6-tetrafluorobenzene or thieno[3,4-c]pyrrole-4,6-dione to form donor-acceptor type pi-conjugated polymers with high molecular weights in almost quantitative yields.
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