间位/对位共轭拓扑调控顺式/反式四硼发色团的单重态与三重态光物理性质

doi:10.1016/j.actphy.2026.100400

摘要/Abstract

摘要： 调控单重态辐射衰减与三重态布居的竞争关系，是无重原子有机发色团物理化学领域的核心研究问题。本文报道了两对含四硼的顺式/反式结构异构体，系统研究了分子构型以及由有效连接方式决定的间位/对位共轭拓扑对激发态行为的调控作用。间位顺式异构体通过中心亚苯基连接单元形成间位连接的交叉共轭路径，分子整体构型相对平面，固态下呈交叉堆积排列，因此在溶液与凝聚态中均表现出强荧光发射。与之相反，反式异构体为对位连接的线性共轭路径，具有更窄的光学/电化学带隙，吸收与发射光谱红移，荧光量子产率更低，非辐射衰减过程显著增强。纳秒瞬态吸收光谱结果显示，对位反式异构体存在长寿命三重态特征信号，寿命最长可达79.1 μs；而相同测试条件下，间位顺式异构体未观测到明显的长寿命瞬态吸收信号。进一步研究发现，对位反式异构体具备高效的单线态氧生成能力，可作为可见光光敏剂应用于三组分自由基光聚合体系。晶体结构解析、稳态光谱、瞬态吸收、电化学测试、活性氧检测及理论计算的结果共同佐证了一种拓扑辅助的激发态调控机制：在共轭拓扑、分子构型、窄化激发态带隙与非辐射衰减动力学的协同作用下，间位顺式分子骨架更有利于单重态的辐射弛豫，而对位反式骨架更有利于实现长寿命三重态的有效布居。本工作证实，有效共轭拓扑可作为调控无重原子含硼发色团单重态与三重态光功能的重要分子参数。

关键词: 四硼发色团, 结构异构, 共轭拓扑, 激发态动力学, 光聚合

Abstract: Regulating the competition between radiative singlet-state decay and triplet-state population is a central issue in the physical chemistry of heavy-atom-free organic chromophores. Herein, we report two pairs of tetra-boron-containing cis/trans structural isomers, and investigate how configurational geometry and effective connectivity-dependent meta/para conjugation topology regulate their excited-state behaviors. The m-Cis isomers possess a meta-connected cross-conjugated pathway through the central phenylene linker, together with relatively planar molecular geometries and cross-packed solid-state arrangements, giving intense fluorescence in solution and in the condensed state. In contrast, the p-Trans isomers feature a para-connected, more linearly conjugated pathway, narrowed optical/electrochemical gaps, red-shifted absorption and emission, lower fluorescence quantum yields, and enhanced nonradiative decay. Nanosecond transient absorption spectroscopy reveals long-lived triplet-state signatures for the p-Trans isomers with lifetimes up to 79.1 μs, whereas the m-Cis isomers show no obvious long-lived transient absorption under the same conditions. The p-Trans isomers further exhibit efficient singlet oxygen generation and serve as visible-light sensitizers in three-component free-radical photopolymerization systems. Combined crystallographic, steady-state spectroscopic, transient absorption, electrochemical, ROS-detection, and theoretical results support a topology-assisted excited-state regulation mechanism, in which the m-Cis framework favors radiative singlet-state relaxation, while the p-Trans framework favors access to long-lived triplet states through the interplay of conjugation topology, molecular geometry, narrowed excited-state gaps, and nonradiative decay kinetics. This work highlights effective conjugation topology as a useful molecular parameter for tuning singlet and triplet photofunctions in heavy-atom-free boron-containing chromophores.

Key words: Tetra-boron chromophores, Structural isomerism, Conjugation topology, Excited-state dynamics, Photopolymerization

尚英建, 于长江, 程超, 孙启可, 许新胜, 魏亚雄, 许洋洋, 赵学峰, 焦莉娟, 郝二红, 缪伟. 间位/对位共轭拓扑调控顺式/反式四硼发色团的单重态与三重态光物理性质[J]. 物理化学学报 2026, (), 100400. doi: 10.1016/j.actphy.2026.100400

Yingjian Shang, Changjiang Yu, Chao Cheng, Qike Sun, Xinsheng Xu, Yaxiong Wei, Yangyang Xu, Xuefeng Zhao, Lijuan Jiao, Erhong Hao, Wei Miao. Meta/para conjugation topology regulates singlet and triplet photophysics in cis/trans tetra-boron chromophores[J]. Acta Phys. -Chim. Sin. 2026, (), 100400. doi: 10.1016/j.actphy.2026.100400

链接本文: https://www.whxb.pku.edu.cn/CN/10.1016/j.actphy.2026.100400

https://www.whxb.pku.edu.cn/CN/Y2026/V/I/100400

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