Origin of the Zero-Field Splitting in Mononuclear Octahedral MnIV Complexes: A Combined Experimental and Theoretical Investigation

详细信息    查看全文

• 作者：Matija Zlatar ; Maja Gruden ; Olga Yu Vassilyeva ; Elena A. Buvaylo ; A. N. Ponomarev ; S. A. Zvyagin ; J. Wosnitza ; J. Krzystek ; Pablo Garcia-Fernandez ; Carole Duboc
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：February 1, 2016
• 年：2016
• 卷：55
• 期：3
• 页码：1192-1201
• 全文大小：597K
• ISSN：1520-510X

文摘

The aim of this work was to determine and understand the origin of the electronic properties of Mn<sup>IVsup> complexes, especially the zero-field splitting (ZFS), through a combined experimental and theoretical investigation on five well-characterized mononuclear octahedral Mn<sup>IVsup> compounds, with various coordination spheres (N<sub>6sub>, N<sub>3sub>O<sub>3sub>, N<sub>2sub>O<sub>4sub> in both trans (trans-N<sub>2sub>O<sub>4sub>) and cis configurations (cis-N<sub>2sub>O<sub>4sub>) and O<sub>4sub>S<sub>2sub>). High-frequency and -field EPR (HFEPR) spectroscopy has been applied to determine the ZFS parameters of two of these compounds, MnL<sup>trans-N2O4sup> and MnL<sup>O4S2sup>. While at X-band EPR, the axial-component of the ZFS tensor, D, was estimated to be +0.47 cm<sup>–1sup> for MnL<sup>O4S2sup>, and a D-value of +2.289(5) cm<sup>–1sup> was determined by HFEPR, which is the largest D-magnitude ever measured for a Mn<sup>IVsup> complex. A moderate D value of ?0.997(6) cm<sup>–1sup> has been found for MnL<sup>trans-N2O4sup>. Quantum chemical calculations based on two theoretical frameworks (the Density Functional Theory based on a coupled perturbed approach (CP-DFT) and the hybrid Ligand-Field DFT (LF-DFT)) have been performed to define appropriate methodologies to calculate the ZFS tensor for Mn<sup>IVsup> centers, to predict the orientation of the magnetic axes with respect to the molecular ones, and to define and quantify the physical origin of the different contributions to the ZFS. Except in the case of MnL<sup>trans-N2O4sup>, the experimental and calculated D values are in good agreement, and the sign of D is well predicted, LF-DFT being more satisfactory than CP-DFT. The calculations performed on MnL<sup>cis-N2O4sup> are consistent with the orientation of the principal anisotropic axis determined by single-crystal EPR, validating the calculated ZFS tensor orientation. The different contributions to D were analyzed demonstrating that the d-d transitions mainly govern D in Mn<sup>IVsup> ion. However, a deep analysis evidences that many factors enter into the game, explaining why no obvious magnetostructural correlations can be drawn in this series of Mn<sup>IVsup> complexes.