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Rational Self‐Assembly of Tricobalt Extended Metal Atom Chains and [MF 6 ] 2– Building Blocks into One‐Dimensional Coordination Polymers
Author(s) -
Cortijo Miguel,
Bulicanu Vladimir,
Pedersen Kasper S.,
Rouzières Mathieu,
Bendix Jesper,
Clérac Rodolphe,
Hillard Elizabeth A.
Publication year - 2018
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201701084
Subject(s) - chemistry , isostructural , crystallography , atom (system on chip) , antiferromagnetism , dimethylformamide , metal , polymer , coordination polymer , ferromagnetism , crystal structure , condensed matter physics , organic chemistry , physics , solvent , computer science , embedded system
Following our recent work on the first crystallographically characterized coordination polymers based on tricobalt extended metal atom chains (EMACs), namely, [Co 3 (dpa) 4 MF 6 ] · 2DMF [M = Zr IV ( 1 ), Sn IV ( 2 ), and Re IV ( 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 [Co 3 (dpa) 4 ] 2+ and 5d [MF 6 ] 2– [M = Ir IV ( 4 ) and Os IV ( 5 )] building blocks. These 1D complexes are isostructural and crystallize in the P 4/ 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 {Co 3 } and [MF 6 ] 2– units in 3 and 4 , whereas the nonmagnetic [MF 6 ] 2– linkers of 1 and 5 mediate antiferromagnetic coupling between the {Co 3 } spins. For 2 , no significant exchange coupling was observed. Spin‐crossover behavior, which was observed for the parent [Co 3 (dpa) 4 Cl 2 ] complex, was not detected for 1 – 5 up to 300 K. This work demonstrates that EMACs and [MF 6 ] 2– complexes can be considered as appealing building blocks for the design of new functional coordination networks.