Kumar Jatish, Nakashima Takuya, Tsumatori Hiroyuki, Mori Midori, Naito Masanobu, Kawai Tsuyoshi
Graduate School of Materials Science, Nara Institute of Science and Technology, NAIST, 8916-5 Takayama, Ikoma, Nara 630-0192 (Japan), Fax: (+81) 743-72-6179.
Chemistry. 2013 Oct 11;19(42):14090-7. doi: 10.1002/chem.201302146. Epub 2013 Sep 11.
Chiral bichromophoric perylene bisimides are demonstrated as active materials of circularly polarized emission. The bichromophoric system exhibited circularly polarized luminescence with dissymmetry factors typical of that of similar organic chiral chromophoric systems in the monomeric state. Variation in solvent composition led to the formation of stably soluble helical aggregates through intermolecular interactions. A large enhancement in the dissymmetry of circularly polarized luminescence was exhibited by the aggregated structures both in the solution and solid states. The sum of excitonic couplings between the individual chromophoric units in the self-assembled state results in relatively large dissymmetry in the circularly polarized luminescence, thereby giving rise to enhanced dissymmetry factors for the aggregated structures. The spacer between chiral center and chromophoric units played a crucial role in the effective enhancement of chiroptical properties in the self-assembled structures. These materials might provide opportunities for the design of a new class of functional bichromophoric organic nanoarchitectures that can find potential applications in the field of chiroptical memory and light-emitting devices based on supramolecular electronics.
手性双发色团苝二酰亚胺被证明是圆偏振发光的活性材料。该双发色团体系表现出圆偏振发光,其不对称因子与单体状态下类似有机手性发色团体系的典型不对称因子相同。溶剂组成的变化通过分子间相互作用导致形成稳定可溶的螺旋聚集体。聚集结构在溶液和固态下均表现出圆偏振发光不对称性的大幅增强。自组装状态下各个发色团单元之间的激子耦合总和导致圆偏振发光中相对较大的不对称性,从而使聚集结构的不对称因子增强。手性中心与发色团单元之间的间隔基在自组装结构中手性光学性质的有效增强中起关键作用。这些材料可能为设计一类新型功能性双发色团有机纳米结构提供机会,这类结构在基于超分子电子学的手性光学记忆和发光器件领域具有潜在应用。