Rational self-assembly of tricobalt extended metal atom chains and [MF6]2– building blocks into one-dimensional coordination polymers Article - 2018

Miguel Cortijo, Vladimir Bulicanu, Kasper S. Pedersen, Mathieu Rouzières, Jesper Bendix, Rodolphe Clérac, Elisabeth A. Hillard

Miguel Cortijo, Vladimir Bulicanu, Kasper S. Pedersen, Mathieu Rouzières, Jesper Bendix, Rodolphe Clérac, Elisabeth A. Hillard, « Rational self-assembly of tricobalt extended metal atom chains and [MF6]2– building blocks into one-dimensional coordination polymers  », European Journal of Inorganic Chemistry, numéro spécial Molecular magnetism, 2018, pp. 320-325. ISSN 1434-1948

Abstract

Following our recent work on the first crystallographically characterized coordination polymers based on tricobalt extended metal atom chains (EMACs), namely, [Co3(dpa)4MF6]·2DMF [M = ZrIV (1), SnIV (2), and ReIV (3) ; Hdpa = 2,2′-dipyridylamine ; DMF = N,N′-dimethylformamide], we have generalized our synthetic approach based on robust fluoride complexes to prepare new self-assembled one-dimensional (1D) polymers formed by [Co3(dpa)4]2+ and 5d [MF6]2– [M = IrIV (4) and OsIV (5)] building blocks. These 1D complexes are isostructural and crystallize in the P4/ncc space group such that the fourfold axis is coincident with the metal axes of the rigorously linear chains. Magnetic studies reveal ferromagnetic coupling between the S = 1/2 Co3 and [MF6]2– units in 3 and 4, whereas the nonmagnetic [MF6]2– linkers of 1 and 5 mediate antiferromagnetic coupling between the Co3 spins. For 2, no significant exchange coupling was observed. Spin-crossover behavior, which was observed for the parent [Co3(dpa)4Cl2] complex, was not detected for 1–5 up to 300 K. This work demonstrates that EMACs and [MF6]2– complexes can be considered as appealing building blocks for the design of new functional coordination networks.

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