Li Sheng-Yong, Sun Zuo-Bang, Zhao Cui-Hua
School of Chemistry and Chemical Engineering, Key Laboratory of Special Functional Aggregated Materials, Ministry of Education, Shandong University , Jinan 250100, People's Republic of China.
Inorg Chem. 2017 Aug 7;56(15):8705-8717. doi: 10.1021/acs.inorgchem.6b02847. Epub 2017 Feb 6.
Triarylboranes have attracted significantly increasing research interest as a remarkable class of photoelectronic π-electron materials. Because of the presence of vacant p orbital on the B center, the boryl group is a very unique electron acceptor that exhibits not only electron-accepting ability through p-π* conjugation but also high Lewis acidity to coordinate with Lewis bases and steric bulk arising from the aryl substituent on the B center to get enough kinetic stability. Thus, the incorporation of a trivalent B element into π-conjugated systems is an efficient strategy to tune the electronic and stereo structures and thus the photoelectronic properties of π-electron systems. When an electron-donating group, such as amino, is present, triarylboranes would likely display intramolecular charge-transfer transitions. These kinds of molecules are often highly emissive. In addition, the geometry of the molecules has a great impact on the emission properties. In this Forum Article, we herein describe our recent progress on the charge-transfer emitting triarylborane π-electron systems with novel geometries, which include the lateral boryl-substituted π-system with amino groups at the terminal positions, the o,o'-substituted biaryl π-system with boryl and amino groups at the o,o'-positions, a triarylborane-based BODIPY system, and a B,N/S-bridged ladder-type π-system. We mainly put the emphasis on the molecular design concept, structure-property relationships, intriguing emission properties and great applications of the corresponding triarylborane π-systems.
作为一类卓越的光电π电子材料,三芳基硼烷已引起了越来越多的研究兴趣。由于硼中心存在空的p轨道,硼基是一种非常独特的电子受体,它不仅通过p-π*共轭表现出电子接受能力,而且具有高路易斯酸性以与路易斯碱配位,并且硼中心上的芳基取代基产生的空间位阻使其具有足够的动力学稳定性。因此,将三价硼元素引入π共轭体系是调节电子和立体结构以及π电子体系光电性质的有效策略。当存在诸如氨基等供电子基团时,三芳基硼烷可能会显示分子内电荷转移跃迁。这类分子通常具有很强的发光性。此外,分子的几何形状对发光性质有很大影响。在这篇论坛文章中,我们在此描述了我们在具有新颖几何形状的电荷转移发光三芳基硼烷π电子体系方面的最新进展,其中包括在末端位置带有氨基的侧向硼基取代π体系、在o,o'-位置带有硼基和氨基的o,o'-取代联芳基π体系、基于三芳基硼烷的BODIPY体系以及B,N/S桥连的梯型π体系。我们主要强调了相应三芳基硼烷π体系的分子设计概念、结构-性质关系、有趣的发光性质和重要应用。