4-甲基-BODIPY衍生物的X射线光电子能谱和量子化学分析

XPS and quantum chemical analysis of 4Me-BODIPY derivatives.

作者信息

Tikhonov Sergey A, Sidorin Andrey E, Ksenofontov Alexander A, Kosyanov Denis Yu, Samoilov Ilya S, Skitnevskaya Anna D, Trofimov Alexander B, Antina Elena V, Berezin Mikhail B, Vovna Vitaliy I

机构信息

Kamchatka Branch of the Geophysical Survey of the Russian Academy of Sciences, Piip blvd. 9, 683023 Petropavlovsk-Kamchatsky, Russian Federation.

Far Eastern Federal University, 10 Ajax Bay, Russky Island, 690922 Vladivostok, Russian Federation.

出版信息

Phys Chem Chem Phys. 2023 Feb 8;25(6):5211-5225. doi: 10.1039/d2cp04541a.

DOI:10.1039/d2cp04541a

PMID:36723097

Abstract

The results of a X-ray photoelectron spectroscopy (XPS) and steady-state absorption spectroscopy study of the electronic structure, and cationic and excited states of a series of 1,3,5,7-tetramethyl-substituted BODIPYs (4Me,2R-BODIPYs) are presented. The experimental data were interpreted using high-level quantum chemical computations, including the algebraic diagrammatic construction method for the polarization propagator of the second order (ADC(2)), the outer-valence Green's function (OVGF) method, the density functional (DFT) approach, and the time-dependent DFT (TD-DFT) approach. Substitution effects on the XPS and absorption spectra were determined for 2,6-positions of 4Me,2R-BODIPY pyrrole nuclei (R = H, Br, Bu, benzyl). A very satisfactory performance of the DFT Koopmans theorem analogue was demonstrated with respect to the energy intervals between the electronic levels of 4Me,2R-BODIPY above 13 eV (BHHLYP functional) and the values of the HOMO-LUMO energy gap (ωB97X functional).

摘要

本文展示了对一系列1,3,5,7-四甲基取代的BODIPY（4Me,2R-BODIPY）的电子结构、阳离子态和激发态进行的X射线光电子能谱（XPS）和稳态吸收光谱研究的结果。利用高级量子化学计算对实验数据进行了解释，这些计算方法包括二阶极化传播子的代数图示构造方法（ADC(2)）、外价格林函数（OVGF）方法、密度泛函（DFT）方法和含时密度泛函（TD-DFT）方法。确定了4Me,2R-BODIPY吡咯核2,6-位（R = H、Br、Bu、苄基）对XPS和吸收光谱的取代效应。在高于13 eV的4Me,2R-BODIPY电子能级之间的能量间隔（BHHLYP泛函）以及HOMO-LUMO能隙值（ωB97X泛函）方面，DFT库普曼斯定理类似物表现出非常令人满意的性能。