基于Ru-C构筑的近红外单核及多核钌配合物的合成及光电化学性质研究

项目名称： 基于Ru-C构筑的近红外单核及多核钌配合物的合成及光电化学性质研究

项目编号： No.21301196

项目类型： 青年科学基金项目

立项/批准年度： 2014

项目学科： 数理科学和化学

项目作者： 李襄宏

作者单位： 中南民族大学

项目金额： 25万元

中文摘要： 设计合成光吸收强、吸收光谱范围宽、光稳定性好且能级合适的染料敏化剂一直是染料敏化纳米晶太阳能电池（DSSC）领域的一个研究热点。基于C∧N-配位的环金属化钌配合物由于 Ru-C 键的形成，其对长波方向的光捕获能力明显强于N∧N－配位的钌多联吡啶配合物。本课题拟从提高配合物的HOMO能级（采用C∧N-配位模式）和降低配合物的LUMO能级(增加吡啶类配体的共轭程度)两个方面设计合成在长波方向具有强光吸收的单核环金属化钌配合物，并在此基础上设计在可见-近红外区有强吸收的钌同或杂多核配合物，使它们的长波方向吸光强度达到20,000 M-1cm-1。在研究这些配合物的分子结构与电子吸收光谱关系的基础上，选择将光吸收强、吸收范围宽且能级与TiO2导带能级相匹配的配合物敏化到TiO2 纳米薄膜上，研究其结构与光敏化性质之间的关系，为探索合成具有优良性能的光敏化剂提供新思路和方法。

中文关键词： 环金属钌配合物；MLCT态吸收；摩尔消光系数；光物理性质；合成与表征

英文摘要： The design of sensitizers with wide absorption range, high molar absorption coefficient of the MLCT bands and long-term photo-stability is attractive in dye-sensitized solar cells, which also should have appropriate energy level matched with TiO2. This proposal aims to synthesize some mononuclear cyclometalated ruthenium complexes which have strong absorptions at longer wavelengths. Two approaches will be used to expand and enhance the light absorptions of these complexes. The one is to increase the highest occupied molecular orbital （HOMO）level by the replacement of a neutral Ru-N bond with an anionic Ru-C bond, and the other is to lower the lowest unoccupied molecular orbital (LUMO) level by increasing the conjugation length of the bipyridyl ligands. Then, multinuclear（homonuclear or heteronuclear） ruthenium complexes with strong absorptions closer to visible-near infrared region will be synthesized based on these selected mononulcear cyclometalated ruthenium complexes. The expecting molar extinction coefficients of all these complexes will reach at or above 20,000 M-1cm-1. The relationships between the molecular structures and their corresponding electronic absorption spectra will be investigated. And then, a complex with stronger and wider absorptions at longer-wavelength will be selected and sensitized ont

英文关键词： cyclometallated ruthenium complexes；MLCT absorptions；molar extinction coefficients；photophysical properties；sythesis and characterization