Bifunctional 1,2,4-triazole-carboxylate ligands, an achiral 1,2,4-triazol-4-yl-acetic acid (trgly-H) and a chiral (d)-2-(1,2,4-triazol-4-yl)-propionic acid (d-trala-H), derived from the corresponding alpha-amino acid precursors revealed unique binding abilities in the construction of Cu(II)-coordination polymers composing discrete triangular [Cu-3(mu(3)-OH)] clusters. A related series of MOFs, [Cu-3(mu(3)-OH)(trgly)(3)(SO4)]center dot 2H(2)O (1a), [Cu-3(mu(3)-OH) (trgly)(3)(H2O)(3)]SO4 center dot 16H(2)O (1b), Cu-3(mu(3)-OH)(d-trala)(3)(ClO4)(0.5)](ClO4)(1.5)center dot 1.5H(2)O (2), was prepared, and their crystal structures were determined by means of X-ray diffraction. Being singly deprotonated, the organic ligands act as multidentate mu(3)- or mu(4)- donors using tr and -COO- moieties. The generated [Cu-3(mu(3)-OH)(tr)(3)] cluster core is primarily supported by three [-N-N-] triazole heterocycles in a basal plane and tripodal-assisted mu(3)-anions (SO42-: 1a; ClO4-: 2) capping the axial faces. The carboxylate groups join the units into either two-dimensional (2D) layer (1a, 2) or 3D zeolite-like networks (1b). Compound 1b represents the topology of alpha-Po (pcu: 4(12).6(3)) and crystallizes in the noncentrosymmetric space group I (4) over bar 3m, in which the six-connected [Cu-3(mu(3)-OH)] clusters and trgly self-assemble in an open-channel cubic array possessing similar to 56% solvent-accessible volume. Upon slight thermal treatment (similar to 60 degrees C), the structure irreversibly shrinks to the nonporous 2D motif la that belongs to a uninodal (3,6) network type. In structure 2 (space group R3(2)), due to the [-N-N-] triazole and 1,3-bidentate carboxylate binding mode, each organic ligand bridges three metal clusters affording cross-linking of two adjacent layers with the same (3,6) topology. The resultant 3,9-c net is novel and can be categorized as two-nodal with point symbol {4(18).6(18)}{4(2).6}(3). Spin frustration and antisymmetric exchange effects, resulting in abnormally low g values in the S = 1/2 states, were observed in the magnetic properties and the EPR spectra.