Solvent/Anion -Induced Structural Modification in a Discrete {Co14} Clusters

We present here a nested [Co4Co10] cluster consist of an inner [Co4(μ3-OH)4] cubane and a [Co10(dpbt)6Cl12] adamantane periphery, formulated as [Co14(μ3-OH)4(dpbt)6Cl12]·14CH3CH2OH (1) (here, H2dpbt ligand= 5,5'-di(pyridin-2-yl)-3,3'-bi(1,2,4-triazole)). After suitable modifications in the aspects of solvent and substitutional anion reaction conditions, three crystalline {Co14} cluster with the same skeleton of 1 formulated as: [Co14(μ3-OH)4(dpbt)6Cl12]·11CH3CN (2), [Co14(μ3-OH)4(dpbt)6Cl12]·6CH3CH2COCH3 (3), and [Co14(μ3-OH)4(dpbt)6Cl12]·4CH3COCH3 (4); and a bromo-derivative {Co14} cluster: [Co14(μ3-OH)4(dpbt)6Br12]·4CH3CH2OH (5), consist of an [Co10(dpbt)6Br12] adamantane periphery, respectively. The procedure of the structural modification from 1 to 4, can be intuitionally tracked by Scanning Electron Microscope (SEM). Besides, all the compounds 1-5 exhibit spin-glass-like relaxation between 3-12 K, as well as canted antiferromagnetic behavior with the canting angles of 1.27, 0.32, 1.89, 0.20 and 0.24...