p-tert-Butylthiacalix[4]arene-supported high-nuclearity {Co24M8} (M=Mo or W) nanospheres and the hybrids with Keggin polyoxometalates.

Two hybrid assemblies (3 and 4) with two kind of nanoscaled cluster units, the spherical [Co(24)(TC4A)(6)(MO(4))(8)Cl(6)](2+) cation (1 and 2) and Keggin-type [PM(12)O(40)](3-) anion (M = Mo (1/3), W (2/4)), were solvothermally prepared and characterized, in which the spherical units are constructed by six Co(4)-p-tert-butylthiacalix[4]arene (Co(4)-TC4A) SBUs linked by eight MO(4) tetrahedrons and present the highest nuclearity bimetallic clusters capped by cailxarenes. © The Royal Society of Chemistry 2011