Change in the Electronic Structure of the Cobalt(II) Ion in a One-Dimensional Polymer with Flexible Linkers Induced by a Structural Phase Transition

Abstract

A new 1D-coordination polymer [Co(Piv)₂(NH₂(CH₂)₆NH₂)]_n (1, Piv is Me₃CCO₂^- anion) was obtained, the mononuclear fragments {Co(O₂CR)₂} within which are linked by μ-bridged molecules of hexamethylenediamine (NH₂(CH₂)₆NH₂). For this compound, two different monoclinic C2/c (α-1) and P2/n (β-1) phases were found at room temperature by single-crystal X-ray diffraction analysis, with a similar structure of chains and their packages in unit cells. The low-temperature phase (γ-1) of crystal 1 at 150 K corresponds to the triclinic space group P-1. As the temperature decreases, the structural phase transition (SPT) in the α-1 and β-1 crystals is accompanied by an increase in the crystal packing density caused by the rearrangements of both H-bonds and the nearest ligand environment of the cobalt atom ("octahedral CoN₂O₄ around the metal center at room temperature" → "pseudo-tetrahedral CoN₂O₂ at 150 K"). The SPT was confirmed by DSC in the temperature range 210-150 K; when heated above 220 K, anomalies in the behavior of the heat flow are observed, which may be associated with the reversibility of SPT; endo effects are observed up to 300 K. The SPT starts below 200 K. At 100 K, a mixture of phases was found in sample 1: 27% α-1 phase, 61% γ-1 phase. In addition, at 100 K, 12% of the new δ-1 phase was detected, which was identified from the diffraction pattern at 260 K upon subsequent heating: the a,b,c-parameters and unit cell volume are close to the structure parameters of γ-1, and the values of the α,β,γ-angles are significantly different. Further heating leads to a phase transition from δ-1 to α-1, which both coexist at room temperature. According to the DC magnetometry data, during cooling and heating, the χ_MT(T) curves for 1 form a hysteresis loop with ~110 K, in which the difference in the χ_MT values reaches 9%. Ab initio calculations of the electronic structure of cobalt(II) in α-1 and γ-1 have been performed. Based on the EPR data at 10 K and the ab initio calculations, the behavior of the χ_MT(T) curve for 1 was simulated in the temperature range of 2-150 K. It was found that 1 exhibits slow magnetic relaxation in a field of 1000 Oe.

Keywords: cobalt(II) complex; dynamic crystals; orbital angular momentum; slow magnetic relaxation; structural phase transition.