A series of trinuclear copper(II) complexes of general formula A(6)[Cu3L2]center dot nH(2)O [L = benzene-1,3,5-tris(oxamate); A = Li+ (n = 8), 1a; Na+ (n = 11.5), 1b; and K+ (n = 8.5), 1 c] have been synthesized, and they have been structurally and magnetically characterized. X-ray diffraction on single crystals of 1c shows the presence of three square-planar copper(II)-bis(oxamato) moieties which are connected by a double benzene-1 3,5-triyl skeleton to give a unique metallacyclophane-type triangular cage. The copper basal planes are virtually orthogonal to the two benzene rings, which adopt an almost perfect face-to-face alignment. Complexes 1 a-c exhibit a quartet (S = 3/2) ground spin state resulting from the moderate ferromagnetic coupling (J values in the range of +7.3 to + 16.5 cm(-1)) between the three Cull ions across the two benzene-1,3,5-tris(amidate) bridges [H = -J(S-1.S-2 + S-2.S-3 + S3.S1) with S1 = S2 = S3 = S-Cu = 1/2]. Density functional theory calculations on the S = 3/2 Cu-3(II) ground spin state of 1c support the occurrence of a spin polarization mechanism for the propagation of the exchange interaction, as evidenced by the sign alternation of the spin density in the 1,3,5-substituted benzene spacers.