A computational study of structural and magnetic properties of bi- and trinuclear Cu(II) complexes with extremely long Cu–-Cu distances

Описание

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.

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Издание

Журнал: Chemical Physics

Выпуск журнала: Vol. 491

Номера страниц: 48-55

ISSN журнала: 03010104

Авторы

  • Baryshnikov Gleb V. (KTH Royal Inst Technol, Sch Biotechnol, Div Theoret Chem & Biol, S-10691 Stockholm, Sweden; Bohdan Khmelnytsky Natl Univ, Dept Chem & Nanomat Sci, UA-18031 Cherkassy, Ukraine)
  • Minaev Boris F. (Bohdan Khmelnytsky Natl Univ, Dept Chem & Nanomat Sci, UA-18031 Cherkassy, Ukraine)
  • Baryshnikova Alina T. (Bohdan Khmelnytsky Natl Univ, Dept Chem & Nanomat Sci, UA-18031 Cherkassy, Ukraine)
  • Agren Hans (KTH Royal Inst Technol, Sch Biotechnol, Div Theoret Chem & Biol, S-10691 Stockholm, Sweden; Siberian Fed Univ, Inst Nanotechnol Spect & Quantum Chem, Krasnoyarsk 660041, Russia)

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