Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University Katsura, Nishikyo-ku, Kyoto 615-8510, Japan.
Phys Chem Chem Phys. 2023 Apr 26;25(16):11839-11844. doi: 10.1039/d3cp00334e.
We synthesized two types of the regioisomers fused by a phenylnaphthalene ring with variable connection points to the -carborane scaffold. In this paper, we describe their photoluminescence (PL) properties and detailed photochemical mechanisms. According to the series of optical measurements, interestingly, they showed different PL characters in terms of wavelength and the dual-emission character despite that they have the common aromatic unit. Variable-temperature PL measurements and quantum chemical calculations suggested that the substitution position of aryl groups to -carborane plays an important role in determining the energy barrier to the intramolecular charge-transfer (ICT) state at the S state. Finally, it is revealed that the relative position of the C-C bond of -carborane and the aryl center should be responsible for the photophysical events of aryl--carboranes.
我们合成了两种由苯并萘环连接到 -咔硼烷支架的可变连接点的区域异构体。在本文中，我们描述了它们的光致发光（PL）性质和详细的光化学反应机制。根据一系列的光学测量，有趣的是，尽管它们具有共同的芳基单元，但它们在波长和双发射特性方面表现出不同的 PL 特征。变温 PL 测量和量子化学计算表明，芳基取代基到 -咔硼烷的取代位置在决定 S 态下分子内电荷转移（ICT）态的能垒方面起着重要作用。最后，揭示了 -咔硼烷的 C-C 键和芳基中心的相对位置应该负责芳基--咔硼烷的光物理事件。
