Synthesis, Properties, and Applications of Functional Nano-Sized Conjugated Moleculas

为了开发具有优异功能性的新型纳米分子，我们重点研究了几种新型的高度p-延伸体系;经过精心设计、选择性合成，应用于光伏电池、场效应晶体管、可溶性有机半导体、发光二极管、分子开关、功能染料等各种功能分子基器件中，取得了以下主要成果.基于具有稠合噻吩的卟啉类高效聚光分子，开发了与酞菁具有相同电子结构的新型卟啉衍生物。它们在固态下具有很高的溶解度和自组织能力.长链低聚噻吩在光伏电池中的应用：合成了用碳酸或氰基丙酸锚定末端修饰的低聚噻吩（四聚体、八聚体、十二聚体），并在染料敏化的光伏电池中作为活性染料进行测试。 关于我们 太阳能电池（DSSC）。使用氰基丙酸锚修饰的十二聚体的DSSC在AM 1.5太阳模拟器的照射下获得了4.0%的良好的光伏转换效率.自组装，解决方案prosesible有机半导体高性能OFFERS;我们发现，大，刚性，平面n共轭结构与长烷基链的组合可以得到高度可溶性和自组装有机半导体。通过这种方法，制备出了场效应迁移率高达2.7 cm^2/Vs的溶液处理的OFFEs。基于硫醌齐聚物分子的功能染料：二氰基亚甲基取代的硫醌齐聚物被成功地合成到六聚体。取决于低聚硫醌链的长度，低聚物的吸收带通过可见光区（二聚物和二聚物）从UV（单体）转移到近IR（四聚物）。有趣的是，五聚体和六聚体再次显示出可见光区的吸收带。这些现象的实验和理论合理化的结合开壳香料的贡献的“oligothiophene”结构，而不是“oligothionoquinoid”结构。少

In order to develop novel nano-sized molecules showing distinguished functionalities, we focused on several new highly p-extended systems; they were carefully designed, selectively synthesized, and applied to various functional molecular-based devices such as photovoltaic cells, field-effect transistors, soluble organic semiconductors, light emitting diodes, molecular switches, functional dyes, and so on. Followings are major achievements in this project.1. Highly efficient light-condensing molecules based on polphyradines possessing condensed thiophenes; the new polphyradine derivatives that have the same electronic structure with phthalocyanines were developed. They have high solubility and capability of self-organization in the solid state.2. Application of long oligothiophenes to photovoltaic cells: oligothiophenes (tetramer, octamer, dodecamer) modified with a carbonic acid or a cyanopropanoic acid anchoring terminal were synthesized and tested as active dyes in the dye-sensitized … More solar cells (DSSCs). The DSSCs using the dodecamer modified with a cyanopropanoic acid anchor gave good photovoltaic conversion efficiency of 4.0% under the illumination of AM1.5 solar simulator.3. Self-assembling, solution prosessible organic semiconductors for high performance OFETs; we found that combination of large, rigid, and planer n-conjugated structures with long alkyl chains can give highly soluble and self-assembling organic semiconductors. With this approach, solution-processed OFETs with field-effect mobility as high as 2.7 cm^2/Vs were achieved.4. Functional dyes based on oligothionoquinoid molecules: dicyanomethylene-substituted oligothionoquinoids were successfully synthesized up to the hexamer. Depending on the length of the oligothionoquinoid chain, the absorption bands of the oligomers shift from UV (monomer) to near IR (tetramer) via visible regime (dimes and Mimes). Interestingly, pentamer and hexamer showed absorption bands in the visible regime again. These phenomena were experimentally and theoretically rationalized by incorporation of open-shell spices which have contribution of the "oligothiophene" structure rather than the "oligothionoquinoid" structure. Less