Artificial amino acids in nickel(II) and nickel(II)/lanthanide(III) chemistry

The synthesis and magnetic properties of five new homo- and heterometallic nickel(II) complexes containing artificial amino acids are reported: Ni(4)(aib)(3)(aibH)(3)(NO(3))](NO(3))(4)·3.05MeOH (1·3.05MeOH), Ni(6)La(aib)(12)](NO(3))(3)·5.5H(2)O (2·5.5H(2)O), Ni(6)Pr(aib)(12)](NO(3))(3)·5.5H(2)O (3·5.5H(2)O), Ni(5)(OH)(2)(l-aba)(4)(OAc)(4)]·0.4EtOH·0.3H(2)O 6(4·0.4EtOH·0.3H(2)O), and Ni(6)La(l-aba)(12)]La(2)(NO(3))(9)] (5; aibH = 2-aminoisobutyric acid; l-abaH = l-2-aminobutyric acid). Complexes 1 and 4 describe trigonal-pyramidal and square-based pyramidal metallic clusters, respectively, while complexes 2, 3, and 5 can be considered to be metallocryptand-encapsulated lanthanides. Complexes 4 and 5 are chiral and crystallize in the space groups I222 and P2(1)3, respectively. Direct-current magnetic susceptibility studies in the 2-300 K range for all complexes reveal the presence of dominant antiferromagnetic exchange interactions, leading to small or diamagnetic ground states.