Tuning of the height of energy barrier between locally-excited and charge transfer states by altering the fusing position of o-carborane in phenylnaphthalene
Tuning of the height of energy barrier between locally-excited and charge transfer states by altering the fusing position of o-carborane in phenylnaphthalene
复制标题
通过改变邻碳硼烷在苯基萘中的熔合位置来调节局部激发态和电荷转移态之间的能垒高度
DOI：
10.1039/d3cp00334e
复制
发表时间：
2023
影响因子：
3.3
通讯作者：
Chujo Yoshiki
中科院分区：
文献类型：
--
作者：
Ochi Junki;Yanagihara Takumi;Tanaka Kazuo;Chujo Yoshiki
我们合成了两种类型的区域异构体，由一个具有可变连接点的苯萘环与邻碳硼烷支架融合。本文描述了它们的光致发光特性和详细的光化学机理。根据一系列的光学测量，有趣的是，尽管它们具有共同的芳香单元，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，芳基对邻碳硼烷的取代位置对S1态分子内电荷转移（ICT）态的能垒起重要作用。最后，揭示了邻碳硼烷的C-C键与芳基中心的相对位置可能是芳基-邻碳硼烷的光物理事件的原因。
We synthesized two types of the regioisomers fused by a phenylnaphthalene ring with variable connection points to the o-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 o-carborane plays an important role in determining the energy barrier to the intramolecular charge-transfer (ICT) state at the S1 state. Finally, it is revealed that the relative position of the C–C bond of o-carborane and the aryl center should be responsible for the photophysical events of aryl-o-carboranes.