Ring-current aromaticity in open-shell systems |
| |
Authors: | A Soncini PW Fowler |
| |
Institution: | aDepartment of Chemistry, Katholieke Universiteit Leuven, Celestijnenlaan 200F, B-3001 Heverlee, Belgium;bDepartment of Chemistry, University of Sheffield, S3 7HF, UK |
| |
Abstract: | The ab initio ipsocentric approach to calculation and mapping of induced orbital current density is extended to open-shell π systems. ROHF/6-31G** calculations document the (magnetic) aromaticity of planar 4nπ triplet states of 4π/8π annulenes and isobenzofulvene, and quintet excited-state azulene. An orbital model for currents rationalises the generalised form of Baird’s rules, by which 4n + 2 annulenes are aromatic (antiaromatic) in states of even (odd) total spin (vice versa for 4nπ annulenes). In contrast to geometric criteria, ring-currents predict antiaromaticity for the doublet naphthalene radical anion. |
| |
Keywords: | |
本文献已被 ScienceDirect 等数据库收录! |
|