Yang Jun-Cheng, Chen Ke, Zhang Guo-Ling, Qi Chunxuan, Feng Hai-Tao, Tang Ben Zhong
AIE Research Center, Shaanxi Key Laboratory of Phytochemistry, College of Chemistry and Chemical Engineering, Baoji University of Arts and Sciences Baoji Shaanxi 721013 China
School of Science and Engineering, Shenzhen Institute of Aggregate Science and Technology, The Chinese University of Hong Kong Shenzhen 518172 China
Chem Sci. 2025 Feb 5;16(11):4741-4748. doi: 10.1039/d4sc07689c. eCollection 2025 Mar 12.
Constructing supramolecular artificial light-harvesting systems (ALHSs) based on the Förster resonance energy transfer (FRET) mechanism provides an optimal platform for understanding natural photosynthesis and simulating natural light-harvesting systems. In the present work, rigid macrocycle K-1 with a nonplanar conformation and aggregation-induced emission (AIE) properties was selected as an energy donor in ALHSs, while the non-cyclic AIEgen K-2 was used for a comparative study. In aqueous solution, an efficient one-step energy-transfer process was established between blue-emitting K-1 and an acceptor (namely PBTB) with orange fluorescence to afford a high energy-transfer efficiency ( ) of up to 82.6%. Notably, bright white light emission can be readily realized. Moreover, the triad FRET system was fabricated through energy transfer from the AIEgens to PBTB, then further transferring the captured energy to the final red-emitting acceptor (namely as Z1), achieving an efficient two-step sequential energy transfer. When the ratio of K-1/PBTB/Z1 assemblies reached 1000 : 40 : 14, the optimal was 66.4%. More importantly, it was found that the ALHS based on macrocycle K-1 showed much higher photocatalytic activity for the cross-dehydrogenative coupling (CDC) reaction. Therefore, the flexibility of this novel supramolecular strategy renders the macrocyclic AIEgen a promising candidate to construct efficient ALHSs for photocatalysis.
基于Förster共振能量转移（FRET）机制构建超分子人工光捕获系统（ALHSs）为理解自然光合作用和模拟自然光捕获系统提供了一个理想平台。在本工作中，选择具有非平面构象和聚集诱导发光（AIE）特性的刚性大环K-1作为ALHSs中的能量供体，同时使用非环状AIEgen K-2进行对比研究。在水溶液中，在发射蓝光的K-1与具有橙色荧光的受体（即PBTB）之间建立了高效的一步能量转移过程，以实现高达82.6%的高能量转移效率（ ）。值得注意的是，可以很容易地实现明亮的白色发光。此外，通过从AIEgens到PBTB的能量转移，然后将捕获的能量进一步转移到最终的红色发射受体（即Z1），构建了三联体FRET系统，实现了高效的两步连续能量转移。当K-1/PBTB/Z1组装体的比例达到1000∶40∶14时，最佳 为66.4%。更重要的是，发现基于大环K-1的ALHS对交叉脱氢偶联（CDC）反应表现出更高的光催化活性。因此，这种新型超分子策略的灵活性使大环AIEgen成为构建用于光催化的高效ALHSs的有前途的候选者。
