The synthesis of the novel macrocyclic octadentate amino-thiophenolate ligand H(2)L2 (3,7,11,19,23,27-hexaaza-33,34-dithiol-15,31-di(tert-butyl)-tricyclo[27,3,1(13.17)]-tetratriaconta-1(32),13,15,17(34),29,30-hexane) and its ability to support binuclear nickel(II) complexes with dithiolato-bridged square-pyramidal Ni(II) ions are reported. H(2)L2 is obtained as the hexahydrobromide salt from a Schiff-base condensation reaction between 1,2-bis(4-tert-butyl-2,6-diformylphenylthio)ethane and bis(3-aminopropyl)amine followed by two successive reductions with NaBH(4) and Na/NH(3). The ligand forms a green, paramagnetic, binuclear nickel(II) complex dication [Ni(II)(2)L2](2+), which can be isolated as a ClO(4)(-) (4) or BPh(4)(-) salt (5). The binuclear nickel(II) complex contains a central N(3)Ni(μ-S)(2)NiN(3) core with two square-pyramidal coordinated Ni(II) ions. The [Ni(2)L2](2+) dication does not bind further coligands, in striking contrast to the behaviour of the parent [Ni(2)L1](2+) dication supported by the smaller (L1)(2-) macrocycle (containing diethylenetriamine in place of the dipropylenetriamine units) which readily binds a variety of other coligands (L') to form bisoctahedral [Ni(2)L1(L')](+) structures. The unusual behaviour of 4 relates to two different N configurations which leads to a steric shielding of the third bridging position by the CH(2)-groups of the dipropylenetriamine chains. An analysis of the temperature-dependent magnetic susceptibility data of 5 reveals the presence of a weak antiferromagnetic exchange interaction between the spins of the nickel(II) ions with a value for the magnetic exchange coupling constant J of -23.5 cm(-1) (H = -2JS(1)S(2)). These results are further substantiated by DFT calculations.