Metal - Mediated Synthetic Routes to Conjugated Polymers

这一奖项授予加州大学伯克利分校的T.Don Tilley教授，由化学系的先进材料和加工计划提供支持。该奖项的主题是金属介导的以硅、锡和锗为基础的共轭聚合物的合成。将探索一系列广泛的第四类金属氢化物化学。将研究金属介导型Sigma化合硅氢化物脱氢偶联的基本机理；将探索用于脱氢偶联和烯烃聚合的新型早期过渡金属催化剂；将制备聚锡烷、超支化聚锡烷和聚硅烷网络并研究其电子性质；将合成和表征基于锆基催化剂的OFDI-YN和二卤代芳烃偶联聚合物。对于每一种新制备的聚合物或低聚物，将采用光物理和电化学研究来评估可能的光学和电子性能。含有金属骨架的新型聚合物通过与传统共轭碳基聚合物完全不同的过程传输电子，并为不寻常的光学和电子行为创造了新的范例。本研究提供了具有电导、电致发光、光导和压电致变色性能的新型材料，在发光二极管、半导体和非线性光学器件中具有潜在的应用前景。

This award to Prof. T. Don Tilley at the University of California at Berkeley is supported by the Advanced Materials and Processing Program in the Chemistry Division. The theme of the award is the metal mediated synthesis of conjugated polymers based on silicon, tin and germanium. A broad range of Group IV metal hydride chemistries will be explored. Fundamental mechanisms of dehydrocoupling of silicon hydrides via metal-mediated sigma metathesis will be investigated; new early transition metal catalysts for dehydrocoupling and olefin polymerizations will be probed; polystannanes, hyperbranched polystannanes and polysilane networks will be prepared and their electronic properties investigated; new polymers based on zirconocene catalyzed coupling ofdi-ynes and dihaloarenes will be synthesized and characterized. For each new polymer or oligomer prepared, photophysical and electrochemical studies will be employed to assess possible optical and electronic properties. New polymers containing metallic backbones transport electrons by a fundamentally different process than traditional conjugated carbon-based polymers and create new paradigms for unusual optical and electronic behaviour. This research provides new materials which will exhibit electrical conductivity, electroluminescence, photoconductivity and piezochromic properties and will have potential application in light emitting diodes, semiconductors and nonlinear optical devices.