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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

Stefan Mebs*†, Beatrice Braun‡, Ramona Kositzki†, Christian Limberg‡, and Michael Haumann*†

† 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.

http://pubs.acs.org/doi/abs/10.1021/acs.inorgchem.5b01822

Synopsis

Two spin-crossover (SCO) compounds [FeII(phen)2(NCS)2 (1) and FeIII(dedtc)3 (2)] were compared using X-ray absorption and emission spectroscopy and quantum-chemical calculations. This provided a comprehensive picture of the molecular, electronic, vibrational, and thermodynamic changes underlying abrupt (in 1) versus gradual (in 2) SCO. SCO in both compounds is governed by vibrational entropy changes, but inter- and intramolecular ligand-mode coupling may enforce cooperative SCO behavior only in1.

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.