Anion encapsulation promoted by anion⋯π interactions in rationally designed hexanuclear antiferromagnetic wheels: synthesis, structure and magnetic properties

The reaction of Kpymca (pymca = pyrimidine-2-carboxylato anion) with MX2·6H2O and tmda (N,N,N′,N′-tetramethylethylenediamine) in 1 : 3 : 3 molar ratio, using a MeOH/water mixture (3 : 1) as solvent, afforded the hexanuclear complexes [M6(µ-pymca)6(tmda)6]X6·4H2O (M = NiII, X = ClO4−1, BF4−2; M = CoII, X = ClO4−3). The reaction of pymca with either Cu(ClO4)2·6H2O or Cu(BF4)2·6H2O did not lead to any definite product. However, in the presence of strong coordinating chloride anions the linear tetranuclear complex [Cu4(µ-pymca)3Cl(H2O)](ClO4)4·4.5H2O 4 could be obtained. The structures of 1–3 are very similar and consist of wheel-shaped hexanuclear [M6(µ-pymca)6(tmda)6]6+ cations, with pseudo-D…