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Eight oxamato-bridged heterotrinuclear NiIICuIINiII complexes of formula {[Ni(H2O)(dpt)]2(mu-Cu(H2O)(opba))} (ClO4)2 (1), {[Ni(H2O)(dien)]2(mu-Cu(pba))}(ClO4) 2·6H2O (2), {[Ni(H2O)(Medpt)]2(mu-Cu(OHpba))} (ClO4)2·4H2O (3), {[Ni(H2O)- (dien)]2(mu-Cu(Me2pba))} (ClO4)2·2.5H2O (4), {[Ni(H2O)(dpt)]2(mu-Cu(Me2pba))} (ClO4)2·2H2O (5), {[Ni(H2O)(dien)]2(mu- Cu(OHpba))}(ClO4)2·4H2O (6), {[Ni2(dpt)2(mu-Cu(H2O) (pba))]2(mu-N3)2}Na2 (ClO4)4·6H2O (7), and {[Cu(H2O)2(dpt)Ni2- (H2O)(dpt)2](mu-H2 Me2pba(2-))}(ClO4)4·3H2O (8) in which opba = o-phenylenbis(oxamato), pba = 1,3- propylenebis(oxamato), OHpba = 2-hydroxy-1,3-propylenebis(oxamato), Me2pba = 2,2-dimethyl-1,3-propylenbis(oxamato), dpt = 3,3?-diaminodipropylamine, dien = 2,2?-diaminodiethylamine, and Medpt = 3,3?-diamino-N-methyldipropylamine were synthesized and characterized. The crystal structures of 1, 7, and 8 were solved. For complex 1, the trinuclear entities are linked by hydrogen bonds forming a one-dimensional system, and for complex 8, the presence of van der Waals interactions gives a one-dimensional system, too. For complex 7, the trinuclear entities are self-assembled by azido ligands, given a hexanuclear system; each of these hexanuclear entities are self-assembled through two [Na(O)3(H2O)3] octahedral-sharing one-edge entities, given a one-dimensional system. The magnetic behavior of complexes 2-7 was investigated by variable-temperature magnetic susceptibility measurements. Complexes 2-6 exhibit the minimum characteristic of this kind of polymetallic species with an irregular spin state structure. The J value through the oxamato bridge varied between -88 cm-1 (for 6) and -111.2 cm-1 (for 5). For complex 7, the values obtained were J1 = -101.7 cm-1 (through the oxamato ligand) and J2 = -3.2 cm-1 (through the azido ligand).
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Reference：
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI