Synthesis and Properties of Complexes with Unusual {Mn III 4 } and {Mn II 4 } Cages

Two types of manganese complexes with [Mn 4 ] cores featuring the unusual distorted cube topology are presented, the first of which comprises new modifications of the reported complex [Mn III 4 (sao) 4 (saoH) 4 ]·3CHCl 3 : [Mn 4 (sao) 4 (saoH) 4 ]·1.32(C 4 H 10 O)·0.43(CH 4 O) ( 1a ) and [Mn(sao) 4 (saoH) 4 ]·0.5(CH 4 O)·0.5(C 2 H 3 N) ( 1b ) sao = salicylaldoxime. The second, 0.55[Mn 4 Cl 4 (C 12 H 9 N 2 O) 4 (CH 3 OH) 2 (H 2 O) 2 ]·0.45[Mn 4 Cl 4 (C 12 H 9 N 2 O) 4 (CH 3 OH) 4 ] ( 2 ), is the first reported case of a {Mn II 4 } core of this topology besides known {Mn III 4 } compounds. Differences between the {Mn II 4 } and {Mn III 4 } situation are discussed, and so far overlooked differences in magnetic properties between different {Mn III 4 } compounds are pointed out.