Lability-controlled syntheses of heterometallic clusters

Graham N Newton; Kiyotaka Mitsumoto; Rong-Jia Wei; Fumichika Iijima; Takuya Shiga; Hiroyuki Nishikawa; Hiroki Oshio

doi:10.1002/anie.201309374

Lability-controlled syntheses of heterometallic clusters

Angew Chem Int Ed Engl. 2014 Mar 10;53(11):2941-4. doi: 10.1002/anie.201309374. Epub 2014 Feb 19.

Authors

Graham N Newton¹, Kiyotaka Mitsumoto, Rong-Jia Wei, Fumichika Iijima, Takuya Shiga, Hiroyuki Nishikawa, Hiroki Oshio

Affiliation

¹ Graduate School of Pure and Applied Sciences, University of Tsukuba, Tennodai 1-1-1, Tsukuba 305-8571 (Japan).

PMID: 24554307
DOI: 10.1002/anie.201309374

Abstract

A bulky bidentate ligand was used to stabilize a macrocyclic [Fe(III)8Co(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)8Co(II)6] species and a [Fe(III)6Fe(II)2Co(III)2Co(II)2] complex, respectively. Lowering the reaction temperatures allowed isolation of [Fe(III)6Fe(II)2Co(III)2Co(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.

Keywords: ETCST; cyanide bridges; heterometallic complexes; mixed-valent compounds; self-assembly.