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Alkoxide bridged Copper(II) Hinokitiolato and Tropolonato Complexes: Polymorphism, Reconstructive Phase Transition, and Magnetic Properties
Author(s) -
Schnitzler Silvia,
Lamberts Kevin,
Speldrich Manfred,
Kögerler Paul,
Englert Ulli
Publication year - 2016
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201500742
Subject(s) - crystallography , alkoxide , antiferromagnetism , magnetic susceptibility , chemistry , methoxide , copper , phase transition , stereochemistry , condensed matter physics , ion , physics , catalysis , biochemistry , organic chemistry
Polymorphism and an unexpected reconstructive phase transition in [Cu(trop)(μ‐OMe)] 2 (trop = tropolonate) were studied by single crystal and powder X‐ray diffraction; the phase transition is associated with a huge hysteresis of ca. 200 °C. In the readily reproducible crystal form, the methoxide‐bridged dinuclear subunits aggregate to infinite chains by longer bonds in the Jahn‐Teller distorted coordination sphere. Analogous alkoxide‐bridged derivatives with the substituted ligand hinokitiol (hino), [Cu(hino)(μ‐O R )] 2 ( R = Me, Et, i Pr) form pairs of dinuclear complexes and aggregate to discrete tetranuclear molecules. The inter‐cation distance patterns are reflected in the magnetic properties of these two structure types: Strong antiferromagnetic coupling within the dinuclear subunits is observed in either case, but susceptibility measurements confirm differences in exchange coupling between neighboring central Cu II atoms.