An α-Keggin polyoxometalate completely constructed from the late transition metal CoII as poly atomElectronic supplementary information (ESI) available: Details of synthesis, a typical procedure for styrene polymerization, Fig. S1-S16. CCDC 779511. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c2dt31896b

We report a catalytic eight-cobalt-capped α-Keggin polyoxoazocobaltite with a highly symmetric structure completely constructed from the late transition-metal Co II as a poly atom, [Co 20 (OH) 24 (MMT) 12 (SO 4 )](NO 3 ) 2 ·6H 2 O ( 1 ) (MMT: 2-mercapto-5-methyl-1,3,4-thiadiazole). To the best of our knowledge, this is the first homometallic Co II magnetic cluster bearing Keggin structure. It can serve as a potential catalyst in the styrene polymerization. We report a catalytic eight-cobalt-capped α-Keggin polyoxoazocobaltite completely constructed from the late transition-metal Co II as a poly atom.