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)42+ and 5d MF62– 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 MF62– units in 3 and 4, whereas the nonmagnetic MF62– 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 MF62– complexes can be considered as appealing building blocks for the design of new functional coordination networks.
Two 1D coordination polymers based on tricobalt extended metal‐atom chains (EMACs) and 5d hexafluoridometallates (M = IrIV, OsIV) are reported. Magnetic studies show the presence of ferromagnetic interactions between the Co3(dpa)42+ (Hdpa = 2,2′‐dipyridylamine) and IrF62– magnetic sites J/kB = +0.13(6) K, whereas the OsF62– units mediate antiferromagnetic interactions J/kB = –1.9(4) K.
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