我室朱军教授在 JACS 上发表论文：Dual Aromaticity in Both the T0 and S1 States: Osmapyridinium with Phosphonium Substituent

文章链接：https://pubs.acs.org.ccindex.cn/doi/10.1021/jacs.8b11564

摘要：

According to Hückel’s and Baird’s rules, cyclic conjugated species are aromatic either in the ground state or in the excited state only. Thus, species with aromaticity in both states (denoted as adaptive aromaticity) are particularly rare. Here we carry out density functional theory calculations on a series of osmapyridine and osmapyridinium complexes (96 species) and find that two of them display adaptive aromatici-ty, which was verified by various aromaticity indices including HOMA, ELF_π, MCI, ACID_π plots and the heat of hydrogenation. Further study reveals that two osmapyridiniums containing one or two phosphonium substituents exhibit the character of the triplet ground state, which was supported by the high-level coupled cluster calculations. Our findings highlight the importance of a transition metal and phos-phoniums in achieving adaptive aromaticity and triplet ground state and may aid the design of organometallics for photochemical and mo-lecular magnetism applications.