Department of Chemistry, Institute for Molecular Science and Fusion Technology, Kangwon National University, Chuncheon, Gangwon 24341, Republic of Korea.
Center for Catalytic Hydrocarbon Functionalizations, Institute for Basic Science (IBS), Daejeon 34141, Republic of Korea.
Dalton Trans. 2023 Jun 13;52(23):8020-8029. doi: 10.1039/d3dt01086d.
Herein, we prepared an -carborane compound (9biAT) linked to a 9,9'-bianthracene moiety at each C9-position. The compound exhibited reddish emission in solid and solution states. The solvatochromism effect and theoretical calculation results for the excited (S) state of 9biAT verified that the emission was attributed to ICT transition. In particular, the structural rigidity and the orthogonal geometry around the carborane enhanced ICT-based emission in the solution state at 298 K, resulting in a considerably high quantum efficiency ( = 86%) in cyclohexane. In addition, both the value and radiative decay constant () gradually decreased with an increase in the polarity of the organic solvent. Theoretical modelling of the charge distribution in the S-optimised geometry revealed that charge recombination in the radiative-relaxation process upon ICT transition could be delayed under polar conditions. Consequently, a high value in the solution state at room temperature can be obtained by maintaining molecular rigidity and controlling the polarity of the environment.
在这里，我们制备了一种 - 碳硼烷化合物（9biAT），其在每个 C9 位置与 9,9'- 蒽基团相连。该化合物在固态和溶液状态下均表现出红色发射。9biAT 的激发（S）态的溶剂化变色效应和理论计算结果证实，发射归因于 ICT 跃迁。特别是，在 298 K 下，碳硼烷周围的结构刚性和正交几何形状增强了溶液状态下基于 ICT 的发射，导致环己烷中的量子效率（ = 86%）相当高。此外， 值和辐射衰减常数（ ）随着有机溶剂极性的增加而逐渐降低。S-优化几何形状中电荷分布的理论建模表明，在 ICT 跃迁过程中，辐射弛豫过程中的电荷复合可以在极性条件下延迟。因此，通过保持分子刚性和控制环境极性，可以在室温下的溶液状态下获得高 值。
