Soluble Diphenylhexatriene Dimers for Intramolecular Singlet Fission with High Triplet Energy.
Soluble Diphenylhexatriene Dimers for Intramolecular Singlet Fission with High Triplet Energy.
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DOI：
10.1021/jacs.2c12060
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发表时间：
2023-02-01
影响因子：
15
通讯作者：
Bronstein, Hugo
中科院分区：
文献类型：
--
作者：
Millington, Oliver;Montanaro, Stephanie;Leventis, Anastasia;Sharma, Ashish;Dowland, Simon A.;Sawhney, Nipun;Fallon, Kealan J.;Zeng, Weixuan;Congrave, Daniel G.;Musser, Andrew J.;Rao, Akshay;Bronstein, Hugo
分子内单重态裂变（iSF）促进单分子激子倍增，将单个分子内的激发单重态转换为一对三重态。确定SF增强光伏设计的可行性的关键参数是三重态能量;许多现有的iSF材料的三重态能量太低，无法通过光子倍增器方案有效转移到硅。在这项工作中，一系列的六个新的二聚体的基础上的高三重态能量，SF-活性发色团，1，6-二苯基-1，3，5-己三烯（DPH）[E（T1）<$1.5 eV]，设计，合成，并进行了表征。瞬态吸收光谱和荧光寿命研究表明，五个二聚体显示iSF活性，单线态裂变的时间常数在7 ± 2 ps和2.2 ± 0.2 ns之间变化，表现最好的二聚体的高三重态产率为163 ± 63%。一个强烈的依赖性的耦合几何的裂变率被证明。对于优化的iSF行为，紧密的空间接近性和最小的通过键通信被发现是至关重要的平衡率的SF对反向复合过程。
Intramolecular singlet fission (iSF) facilitates single-molecule exciton multiplication, converting an excited singlet state to a pair of triplet states within a single molecule. A critical parameter in determining the feasibility of SF-enhanced photovoltaic designs is the triplet energy; many existing iSF materials have triplet energies too low for efficient transfer to silicon via a photon multiplier scheme. In this work, a series of six novel dimers based upon the high-triplet-energy, SF-active chromophore, 1,6-diphenyl-1,3,5-hexatriene (DPH) [E(T1) ∼ 1.5 eV], were designed, synthesized, and characterized. Transient absorption spectroscopy and fluorescence lifetime studies reveal that five of the dimers display iSF activity, with time constants for singlet fission varying between 7 ± 2 ps and 2.2 ± 0.2 ns and a high triplet yield of 163 ± 63% in the best-performing dimer. A strong dependence of the rate of fission on the coupling geometry is demonstrated. For optimized iSF behavior, close spatial proximity and minimal through-bond communication are found to be crucial for balancing the rate of SF against the reverse recombination process.
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