Control of the dual emission behaviour of mu-oxo-bridged Si(IV) corrole dimers by substituent bulkiness
Control of the dual emission behaviour of mu-oxo-bridged Si(IV) corrole dimers by substituent bulkiness
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通过取代基体积控制 mu-氧桥 Si(IV) 咯咯二聚体的双重发射行为
DOI：
10.1039/d2qm00332e
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发表时间：
2022
期刊：
影响因子：
--
通讯作者：
T. Tanaka
中科院分区：
文献类型：
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作者：
K. Yamagata;K. Ueta;A. Nakai;A. Osuka;T. Tanaka
最近有报道称，μ-氧桥接的Si（IV）二聚体根据溶剂粘度表现出双发射性质。本文研究了介芳基取代基对激发态动力学和双发射的控制。新制备并表征了阻碍较小的10-未取代和10-苯基-5,15-双（五氟苯基）- si （IV）二聚体和阻碍较大的5,15-双（五氟苯基）-10-（2,4,6-三甲氧基）苯基- si （IV）二聚体。有趣的是，它们的固态结构是不同的：平行的、反平行的或正交的。相比之下，激发态的能量最小化结构被认为在所有情况下都是平行的，因为具有显著的类准分子稳定化。因此，观察到不同的发射行为和粘度依赖性。
The μ-oxo-bridged dimer of Si(IV) corrole has been recently reported to exhibit dual emissive properties depending on the solvent viscosity. Here we examined the control of the excited-state dynamics and dual emission by meso-aryl substituents. Less hindered 10-unsubstituted and 10-phenyl-5,15-bis(pentafluorophenyl)-Si(IV) corrole dimers and the more hindered 5,15-bis(pentafluorophenyl)-10-(2,4,6-trimethoxy)phenyl-Si(IV) corrole dimer were newly prepared and characterised. Interestingly, their solid-state structures are different: parallel, anti-parallel or orthogonal. In contrast, the energy-minimized structures in the excited state have been suggested to be parallel in all cases owing to the significant excimer-like stabilization. As a result, different emission behaviours and viscosity dependence were observed.