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Abstract
The heterometallic tricapped trigonal prism [MnIII3Na6(TBC[4])3(CO3)(Cl)(dmso)7]·5MeCN ([Mn3Na6]; 1·5MeCN) and the related heterometallic tetracapped square prism [MnIII4MnII2Na6(bisTBC[4])2(CO3)2(Cl)2(dmf)8(MeOH)1.2(H2O)0.8]·6MeCN ([Mn6Na6]; 2·6MeCN), are isolated using p-tBu-calix[4]arene (H4TBC[4]) and 2,2’-bis-p-tBu-calix[4]arene (H8-bisTBC[4]), respectively. In the former the MnIII ions sit in the TBC[4] polyphenolic pockets, forming three Mn-(TBC[4]) metalloligands that cap the square faces of the prism, whose vertices contain the six Na ions. Introduction of the bis-calix[4]arene enables expansion of the main building block from three Mn-TBC[4] metalloligands in 1 to four Mn-TBC[4] metalloligands in 2. The result is the formation of a square prism of Na/MnII ions, with four of the square faces capped with MnIII ions. Dc magnetic susceptibility and magnetisation measurements reveal paramagnetism in 1 and weak antiferromagnetic exchange interactions in 2.
