聚集诱导荧光增强的光致变色材料的合成与性能研究

We will design and synthesize some novel highly photochromic fluorescent materials with aggregation-induced emission enchancement including intrinsic photochromic diarylethene silole derivatives, photochromic phenyl substituted olefins, diphenyl dibenzofulvenes and pyran derivatives photochromic multi-function organic molecules, and their chemical structures and properties will be characterized.We will investigate their photochromic preoperties in solution and in the solid state including photostability, thermal stability, fatigue resistance and photo-conversion quantum yield.Some important problems such as the molecular aggregate behaviors of these photochromic fluorescent compounds in solid state, the mechanism of the fluorescent changes depending on photo-controlled single molecule reaction and the fluorescent chromophores energy controlled by photochromic switching units will be investigated. We will investigate the relationship of molecular design and molecular structure of these photochromic molecules with aggregation-induced emission enchancement. We will explore the energy transform, transfer and relative effect of organic fluorescent photo-controlled materials and their photo-controlled properties. Their all-optical function in aggregate solid state such as reading, writing and erasing also will be investigated. We hope to achieve the fluorescent signal as non-destructive read signal and improve the Signal-to-Noise in super-high density optical information storage and the other application fields.

本项目拟设计、合成具有高性能的基于聚集诱导荧光增强的有机光致变色材料，包括本征型聚集诱导荧光增强的光致变色硅杂环状多烯化合物、聚集诱导荧光增强的二苯基二苯并环二烯发色团的光致变色化合物和聚集荧光增强吡喃型光致变色化合物等多功能有机分子体系，并对其结构与性能表征。研究它们在溶液及固体条件下的光致变色性能，包括光热稳定性，耐疲劳性，光开关环量子产率等。研究有机光致变色分子在溶液及聚集态条件下的荧光发射，光调控对分子聚集态荧光影响的机制，分子开关前后对荧光发射团能量转移调控。研究具有聚集诱导荧光增强有机光致变色化合物的分子设计及构效关系；探索聚集诱导荧光增强有机光致变色材料中能量转换，传递及可控性。研究在固体条件下，有机光致变色聚集诱导荧光增强分子读、写、擦的全光子型功能，实现增强荧光信号作为非破坏读出检测信号，提高检测灵敏度和信噪比，为实现超高密度光信息存储及其它方面应用奠定基础。

本项目旨在合成高性能的聚集诱导荧光增强的有机光致变色材料，对其结构与性能表征及其应用研究。项目执行期间报道了多个新型高性能的聚集诱导荧光增强的有机光致变色功能分子体系，取得了研究目标预期的研究成果。如：合成了基于三苯基乙烯和四苯基乙烯的二噻吩乙烯光致变色荧光分子体系，该类化合物具有良好的光致变色性能和光控聚集诱导荧光发射性能；合成了基于分子间的电荷转移机制的四苯基乙烯的光致变色希夫碱-胆固醇荧光分子体系，该分子在环己烷溶液中形成有机凝胶表现出良好的聚集诱导荧光增强性能和光致变色性能；合成了新型多功能光致变色螺吡喃分子，在溶液中、凝胶态和薄膜中具有良好的光致变色性能，分子聚集自组装形成凝胶手性分子开关，可实现颜色、荧光、手性、和螺旋形貌发生可逆变化。采用新型自由基共聚方法合成了聚集诱导荧光增强的二噻吩乙烯和螺噁嗪光致变色荧光聚合物纳米粒子，制备的纳米微球粒子稳定且均匀。在溶液和薄膜中表现出良好的光致变色性能和光控聚集诱导荧光增强性能。合成了聚集诱导荧光增强的氰基取代二苯乙烯-二噻吩乙烯多功能光致变色荧光分子，其在溶液、聚集态、固体以及聚合物薄膜时的表现出良好的光致变色和荧光光开关性能，构建了可擦除重写的光控信息存储模型，实现了光控形貌聚集和解聚的可逆变化。构建了以聚集诱导荧光增强的四苯基乙烯柱芳烃作为主体分子，以二噻吩乙烯含氰基链三氮唑光致变色化合物为客体分子，成功的实现了主客体分子自组装聚集诱导荧光增强光致变色荧光分子开关，在溶液和固体状态中，该主客体分子都表现出良好的荧光光致变色性能并实现了信息的可擦重写功能。构建了基于双联磺化杯[4]芳烃识别的水相二噻吩乙烯光致变色超分子聚合物。合成了新型多功能开关二噻吩乙烯-罗丹明荧光光致变色功能分子并研究了活细胞成像检测。所有合成的光致变色聚集诱导荧光材料在分子开关、分子探针、分子机器、超高密度信息存储等领域表现出潜在的应用价值。