Тип публикации: статья из журнала
Год издания: 2017
Идентификатор DOI: 10.1016/j.chemphys.2017.04.014
Ключевые слова: Bader analysis, Cu(II) complexes, DFT calculations, Ferromagnetic coupling, Open-shell singlet, Spin-spin exchange, “broken symmetry” approximation
Аннотация: Three recently synthesized copper(II) complexes with aroylhydrazones of trifluoroacetic and benzenecarboxylic acids (Dalton Trans., 2013, 42, 16878) have been computationally investigated by density functional theory within the broken symmetry approximation accounting for empirical dispersion corrections. A topological analysis of Показать полностьюelectron density distributions has been carried out using Bader's “quantum theory of atoms in molecules” formalism. The calculated values of spin-spin exchange for the studied dinuclear complexes indicate a very weak ferromagnetic coupling of the unpaired electrons in good agreement with experimental data. At the same time, the trinuclear copper(II) complex possesses a low-spin doublet ground state with one ferromagnetic and two antiferromagnetic spin projections between the triangular-positioned Cu2+ ions. The estimated values of the coupling constants for the spin-spin exchange in this trinuclear complex are in a good agreement with experimental observations. The calculations support a mechanism of exchange coupling through the aromatic links in these strongly spin-separated systems. © 2017 Elsevier B.V.
Журнал: Chemical Physics
Выпуск журнала: Vol. 491
Номера страниц: 48-55