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

We present here a nested [Co-4 subset of Co-10] cluster consist of an inner [Co-4(mu(3)-OH)(4)] cubane and a [Co-10(dpbt)(6)Cl-1(2)] adamantane periphery, formulated as [Co-14(mu(3)-OH)(4)(dpbt)(6)Cl-1(2)]center dot 14CH(3)CH(2)OH (1) (here, H-2 dpbt 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 {Co-14} clusters with the same skeleton of 1, formulated as [Co-14(mu(3)-OH)(4)(dpbt)(6)Cl-1(2)]center dot 11CH(3)CN (2), [Co-14(mu(3)-OH)(4)(dpbt)(6)O-12]center dot 6CH(3)CH(2)COCH(3) (3), and [Co-14(mu(3)-OH)(4)(dpbt)(6)Cl-12]center dot 4CH(3)COCH(3) (4), and a bromo-derivative {Co-14} cluster, [Co-14(mu(3)-OH)(4)(dpbt)(6)Br-12]center dot 4CH(3)CH(2)OH (5), consist of an [Co-10(dpbt)(6)Br-12] 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 and 12 K, as well as canted antiferromagnetic behavior with the canting angles of 1.27, 0.32, 1.89, 0.20, and 0.24 degrees, respectively.