Quantum Chemical Study of Spin Transitions in the Bimetallic Fe/Co Complexes with the Bis(catecholate) Bridging Ligand

M G Chegerev,A A Starikova,A G Starikov

doi:10.1134/s1070328421090013

M G Chegerev, A A Starikova + Show 1 more

Open Access

https://doi.org/10.1134/s1070328421090013

Copy DOI

Abstract

The computational modeling of the spatial and electronic structures, energy characteristics, and magnetic properties of the bimetallic iron and cobalt complexes with 9,10-dimethyl-9,10-ethano-9,10-dihydro-2,3,6,7-tetrahydroxyanthracene and terminal tris(2-pyridylmethyl)amine bases is performed using the density functional theory method (DFT UTPSSh/6-311++G(d,p)). The chosen tetradentate redox ligand is shown to be a promising precursor for the production of magnetically active compounds. The calculations make it possible to establish a relationship between the relative energies of the electronic isomers of the complexes and the structures of the ancillary N-donor moieties. The coordination compounds prone to the manifestation of spin transitions accompanied by a change in the magnetic properties are revealed.

Highlights

Coordination compounds of metals with redoxactive ligands attract increasing interest of chemists and materials scientists due to their potential use as a basis for devices of molecular electronics and spintronics [1,2,3,4,5,6,7,8,9,10]
The polystable compounds that can be switched between three and more electromeric forms [12,13,14,15,16,17,18,19] are of special interest, since they can be used in storage systems of high-density data or for performing complicated logical operations
It is found that the possibility of rearrangements leading to a change in the magnetic properties and their character are determined by the nature of the metal center (Fe/Co), structure of the redox-active ligand, and type of the nitrogen-containing base

Summary

INTRODUCTION

Coordination compounds of metals with redoxactive ligands attract increasing interest of chemists and materials scientists due to their potential use as a basis for devices of molecular electronics and spintronics [1,2,3,4,5,6,7,8,9,10]. An abundant type of coordination compounds with redox ligands is presented by the salt-like metal complexes containing the o-benzoquinone derivative and ancillary tetradentate nitrogen-containing bases [29,30,31,32,33,34,35,36,37]. It is found that the possibility of rearrangements leading to a change in the magnetic properties and their character are determined by the nature of the metal center (Fe/Co), structure of the redox-active ligand, and type of the nitrogen-containing base. We aimed at enlarging the range of magnetically active compounds and performed the computational modeling of the bimetallic (Fe–Fe and Fe–Co) complexes with tetrahydroxyanthracene L in which tris(2-pyridylmethyl)amine (Тpa) bases (MenТpa, n = 0, 2) played the role of ancillary terminal.

CALCULATION PROCEDURE

RESULTS AND DISCUSSION

CONFLICT OF INTEREST

20. Spin-Crossover Materials