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Anion-Tunable Configuration Isomerism and Magnetic Coupling in a Tetranuclear Discrete, One-Dimensional (1D) Chiral Chain and 1D-Decker Copper(II) Complexes of a Carbohydrazine Derivative

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posted on 06.01.2014, 00:00 by Wei Huang, Yuchao Jin, Dayu Wu, Genhua Wu
The reactions of ligand N′-[(pyridin-2-yl)­methylene]­pyrazine-2-carbohydrazide (ppcd) with different copper salts (1, acetate; 2, perchlorate; 3, sulfate) in MeOH could afford one acetate-bridge tetranuclear discrete [Cu2(ppcd)­(ac)2(H2O)­(OH)]2·H2O (1), one-dimensional (1D) chiral chain [Cu­(ppcd)]­ClO4 (2), and a 1D-decker complex of a trinuclear copper­(II) subunit, Cu3(ppcd)2(H2O)4(SO4)2 (3). Single-crystal X-ray analysis revealed that conformation isomerism of the ppcd ligand was associated with the configuration of −N–N– (trans or cis) and could induce the versatile coordination mode in the presence of different anions. The 1D chiral chain was interestingly obtained from the achiral rigid ligand in complex 2. Magnetic studies indicated that the magnitude of the antiferromagnetic coupling can be tuned because of the configuration isomerism [compound 1 is practically diamagnetic at room temperature (J ≈ −1000 cm–1), with a strong antiferromagnetic one (J = −255.4 cm–1) for 2 in the 1D uniform chain and an antiferromagnetic one (J = −123.6 cm–1) for 3 within the trinuclear copper subunit].