SOMO-HOMO level conversion in triarylmethyl-cored N-heterocyclic carbene-Au(I)complexes triggered by selecting coordination halogens

作     者：Le Zhang Hui-Yu Xie Xin Li Li-Ying Sun Ying-Feng Han 

作者机构：Key Laboratory of Synthetic and Natural Functional Molecule of the Ministry of EducationXi'an Key Laboratory of Functional Supramolecular Structure and MaterialsCollege of Chemistry and Materials ScienceNorthwest UniversityXi'an 710127China 

出 版 物：《Chinese Chemical Letters》 (中国化学快报（英文版）)

年 卷 期：2024年第35卷第11期

页      面：512-516页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 070304[理学-物理化学(含∶化学物理)] 08[工学] 0817[工学-化学工程与技术] 0703[理学-化学] 

基　　金：support from the National Natural Science Fund for Distinguished Young Scholars of China(No.22025107) Shaanxi Fundamental Science Research Project for Chemistry&Biology(No.22JHZ003) the National Youth Top-notch Talent Support Program of China,Xi’an Key Laboratory of Functional Supramolecular Structure and Materials,and the FM&EM International Joint Laboratory of Northwest University 

主　　题：SOMO-HOMO conversion N-heterocyclic carbenes Aufbau and non-Aufbau Electronic structure Halogen atoms Radical 

摘      要：Conventionally,organic radicals adhere to the Aufbau principle,the energy level of the singly occupied molecular orbital(SOMO)is not below the highest occupied molecular orbital(HOMO),but somewhat abnormal phenomena have appeared *** this study,we introduce a novel strategy by incorporating unique NHC-Au-X units into a tris(2,4,6-trichlorophenyl)methyl(TTM)system to create metal-involved open-shell complexes,denoted as TTM-NHC-Au-X(X=I,Br,or Cl).Density-functional theory calculations were used to predict an inversion in the energy of the SOMO and highest doubly occupied molecular orbital(HOMO)of TTM-NHC-Au-I,which is supported by experimental *** radicals TTM-NHC-Au-X demonstrated distinct properties with different coordinated *** radical behaviors have been investigated by EPR,UV-vis spectroscopy and cyclic voltammetry,additional structural information provided by structurally comparing related the precursor complexes given by X-ray ***-NHC-Au-I with SOMO-HOMO conversion(SHC)features a highly thermal decomposition temperature up to 305℃.Furthermore,the photostability of TTM-NHC-Au-I was found to be 75and 23 times greater than that of TTM-NHC-Au-Br and TTM-NHC-Au-Cl,*** findings provide valuable insights into the structural and electronic design principles governing the occurrence of SOMO-HOMO conversion in open-shell systems.