CORTIJO, Miguel; BULICANU, Vladimir; PEDERSEN, Kasper S.; ROUZIÈRES, Mathieu; BENDIX, Jesper; CLÉRAC, Rodolphe; HILLARD, Elisabeth A.

doi:10.1002/ejic.201701084

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CORTIJO, Miguel
Centre de Recherche Paul Pascal [CRPP]
Institut de Chimie de la Matière Condensée de Bordeaux [ICMCB]

BULICANU, Vladimir
Centre de Recherche Paul Pascal [CRPP]

PEDERSEN, Kasper S.
Centre de Recherche Paul Pascal [CRPP]
Institut de Chimie de la Matière Condensée de Bordeaux [ICMCB]

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European Journal of Inorganic Chemistry. 2018 n° 3-4, p. 320-325

Wiley-VCH Verlag

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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.< Réduire

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

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