Abrupt versus Gradual Spin-Crossover in FeII(phen)2(NCS)2 and FeIII(dedtc)3 Compared by X-ray Absorption and Emission Spectroscopy and Quantum-Chemical Calculations
† Institut für Experimentalphysik, Freie Universität Berlin, 14195 Berlin, Germany
‡ Institut für Chemie, Humboldt-Universität zu Berlin, 12489 Berlin, Germany
Inorg. Chem., Article ASAP
DOI: 10.1021/acs.inorgchem.5b01822
Publication Date (Web): December 1, 2015
Copyright © 2015 American Chemical Society
*E-mail: stebs@fu-berlin.de. Phone: +49 30 838 56084. Fax: +49 30 838 56510., *E-mail: michael.haumann@fu-berlin.de. Phone: +49 30 838 56101. Fax: +49 30 838 56510.
Abstract
Molecular spin-crossover (SCO) compounds are attractive for information storage and photovoltaic technologies. We compared two prototypic SCO compounds with FeIIN6 (1, [Fe(phen)2(NCS)2], with phen = 1,10-phenanthroline) or FeIIIS6 (2, [Fe(dedtc)3], with dedtc =N,N′-diethyldithiocarbamate) centers, which show abrupt (1) or gradual (2) thermally induced SCO, using K-edge X-ray absorption and Kβ emission spectroscopy (XAS/XES) in a 8–315 K temperature range, single-crystal X-ray diffraction (XRD), and density functional theory (DFT). Core-to-valence and valence-to-core electronic transitions in the XAS/XES spectra and bond lengths change from XRD provided benchmark data, verifying the adequacy of the TPSSh/TZVP DFT approach for the description of low-spin (LS) and high-spin (HS) species. Determination of the spin densities, charge distributions, bonding descriptors, and valence-level configurations, as well as similar experimental and calculated enthalpy changes (ΔH), suggested that the varying metal–ligand bonding properties and deviating electronic structures converge to similar enthalpic contributions to the free-energy change (ΔG) and thus presumably are not decisive for the differing SCO behavior of 1 and 2. Rather, SCO seems to be governed by vibrational contributions to the entropy changes (ΔS) in both complexes. Intra- and intermolecular interactions in crystals of 1 and 2 were identified by atoms-in-molecules analysis. Thermal excitation of individual dedtc ligand vibrations accompanies the gradual SCO in 2. In contrast, extensive inter- and intramolecular phen/NCS vibrational mode coupling may be an important factor in the cooperative SCO behavior of 1.
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