Enhancing Light‐Absorption and Luminescent Properties of Non‐Emissive 1,3,4,6,9b‐Pentaazaphenalene through Perturbation of Forbidden Electronic Transition by Boron Complexation,Asian Journal of Organic Chemistry

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Enhancing Light‐Absorption and Luminescent Properties of Non‐Emissive 1,3,4,6,9b‐Pentaazaphenalene through Perturbation of Forbidden Electronic Transition by Boron Complexation
Asian Journal of Organic Chemistry ( IF 2.8 ) Pub Date : 2020-01-22 , DOI: 10.1002/ajoc.202000010
Hiroyuki Watanabe ₁ , Yuki Kawano ₁ , Kazuo Tanaka ₁ , Yoshiki Chujo ₁

Affiliation

We report an improvement of optical properties of the non‐emissive molecule through shuffling the molecular orbitals by boron complexation. The 1,3,4,6,9b‐pentaazaphenelene (5AP) derivative having a 2‐(dimesitylboryl)phenyl group was synthesized through a substitution reaction from a 2‐bromophenyl compound. The formation of the B−N dative bond was confirmed by ¹¹B{¹H} NMR spectroscopy and a single‐crystal X‐ray structure analysis. Most of the conventional 5AP derivatives hardly showed emission despite their planar and rigid molecular structures. The previous reports on 5AP derivatives ascribed the non‐luminescent behavior to the forbidden transition between frontier orbitals. On the other hand, the 5AP‐based boron complex in this work showed enhanced light absorption and luminescence from the HOMO−LUMO transition. Theoretical calculations suggested that the boron complexation should play a critical role in perturbing the forbidden character of the HOMO−LUMO transition. Because the nitrogen atom on the 5AP moiety formed the Lewis acid−base pair with the boron atom, the energy level of the HOMO of 5AP was downshifted. The character of the HOMO−LUMO transition of the boron complex was changed to afford the improved optical properties of the boron complex.

中文翻译：

通过硼络合干扰禁忌电子跃迁增强非发光1,3,4,6,9b-五氮杂萘的光吸收和发光性质

我们报道了通过硼络合改组分子轨道改善了非发射性分子的光学性能。通过2-溴苯基化合物的取代反应合成具有2-（二异丁烯丙基）苯基的1,3,4,6,9b-五氮杂萘（5AP）衍生物。通过¹¹ B { ¹证实了BN名词键的形成H} NMR光谱和单晶X射线结构分析。尽管大多数常规5AP衍生物具有平面和刚性分子结构，但几乎不显示发射。先前有关5AP导数的报告将不发光行为归因于边界轨道之间的禁止过渡。另一方面，这项基于5AP的硼配合物显示出来自HOMO-LUMO跃迁的增强的光吸收和发光。理论计算表明，硼络合物应在扰动HOMO-LUMO跃迁的禁忌特性中起关键作用。由于5AP部分上的氮原子与硼原子形成了路易斯酸碱对，因此5AP HOMO的能级降低了。

更新日期：2020-01-23

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