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Lability‐Controlled Syntheses of Heterometallic Clusters
Author(s) -
Newton Graham N.,
Mitsumoto Kiyotaka,
Wei RongJia,
Iijima Fumichika,
Shiga Takuya,
Nishikawa Hiroyuki,
Oshio Hiroki
Publication year - 2014
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201309374
Subject(s) - lability , chemistry , ligand (biochemistry) , cobalt , nickel , cluster (spacecraft) , denticity , spin states , inorganic chemistry , crystallography , crystal structure , organic chemistry , biochemistry , receptor , computer science , programming language
Abstract A bulky bidentate ligand was used to stabilize a macrocyclic [Fe III 8 Co II 6 ] cluster. Tuning the basicity of the ligand by derivatization with one or two methoxy groups led to the isolation of a homologous [Fe III 8 Co II 6 ] species and a [Fe III 6 Fe II 2 Co III 2 Co II 2 ] complex, respectively. Lowering the reaction temperatures allowed isolation of [Fe III 6 Fe II 2 Co III 2 Co II 2 ] clusters with all three ligands. Temperature‐dependent absorption data and corresponding experiments with iron/nickel systems indicated that the iron/cobalt self‐assembly process was directed by the occurrence of solution‐state electron‐transfer‐coupled spin transition (ETCST) and its influence on reaction intermediate lability.