Electrochemical and spectroscopic properties of twisted dibenzo[g,p]chrysene derivatives.
Electrochemical and spectroscopic properties of twisted dibenzo[g,p]chrysene derivatives.
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DOI：
10.3762/bjoc.18.96
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发表时间：
2022
影响因子：
2.7
通讯作者：
Iwasawa, Tetsuo
中科院分区：
文献类型：
--
作者：
Imai, Tomoya;Akasaka, Ryuhei;Yoshida, Naruhiro;Amaya, Toru;Iwasawa, Tetsuo
关键词：
二苯并[g，p]芘（DBC）是一种以萘为核心，四个苯环稠合而成的新型有机电子材料。因此，研究DBC基材料的结构-性能关系对于DBC基材料的设计具有重要意义。在这里，DBC衍生物的电化学和光谱性质进行了研究，并根据密度泛函理论（DFT）计算的取代基和扭转的萘部分的影响进行了检查。所有取代的DBC衍生物都显示出比DBC-H更高的氧化电位，甚至对于含有给电子基团的化合物，如DBC-Me和DBC-SMe。DFT计算清楚地表明，这些较高的氧化电位是由于MeO基团的无效共轭，由于两侧取代基的空间排斥，MeO基团垂直于苯环取向。更具体地，当取代基位于MeO基团的两侧时，MeO基团的诱导效应占主导地位，而不是内消旋效应。关于萘部分的扭转，扭转导致HOMO略微增加和LUMO略微降低。扭曲效应远小于MeO基团的共轭效应。所有取代的DBC衍生物的吸收光谱也显示出红移相比，DBC-H。关于发光，观察到DBC-H和DBC-Si的强光致发光。
Dibenzo[g,p]chrysene (DBC), which consists of a twisted naphthalene core with four fused benzene rings, is a promising framework for organic electronic materials. Therefore, the research for structure–property relationships is important for the design of DBC-based materials. Here, the electrochemical and spectroscopic properties of DBC derivatives were investigated, and the effects of substituents and torsion of the naphthalene moiety were examined based on density functional theory (DFT) calculations. All the substituted DBC derivatives showed higher oxidation potentials than that for DBC-H, even for compounds that contained an electron-donating group such as DBC-Me and DBC-SMe. DFT calculations clearly indicate that these higher oxidation potentials are due to the ineffective conjugation of the MeO group, which is oriented perpendicular to the benzene ring because of the steric repulsion of substituents on both sides. More specifically, the inductive effect of the MeO group is dominant rather than the mesomeric effect when the substituent is located at both sides of the MeO group. Concerning the torsion of the naphthalene moiety, the twisting results in a slight increase in the HOMO and a slight lowering of the LUMO. The twisting effect is much smaller than the conjugation effect of the MeO group. Absorption spectra of all the substituted DBC derivatives also showed a red-shift as compared to that for DBC-H. Concerning the luminescence, a strong photoluminescence was observed for DBC-H and DBC-Si.
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