Eight new multidimensional metal(II) complexes [Zn(tp)₂(NCS)₂ ] (1), [Ni(tp)₂(H₂O)₂(µ-tp)₂Ni(NCS)₄]_n (2), [Co(tp)₂(H₂O)₂(µ-tp)₂Co(NCS)₄]_n (3), [Cd(tp)₂(NCS)₂]_n (4), [Mn(tp)₂(NCS)₂(H₂O)₂] (5), [Zn(tp)₂(NCO)₂] (6), [Cd(tp)(NCO)₂]_n (7) and [Cd(tp)(N₃)₂]_n (8) have been synthesized by conventional reactions of the 1,2,4-triazolo[1,5-a]pyrimidine with metallic(II) salts in the presence of thiocyanate, cyanate and azide as auxiliary ligands. X-Ray diffraction studies on these compounds show that species 1, 5 and 6 are mononuclear units in which zinc and manganese have tetrahedral and octahedral coordination geometry, respectively. Complexes 2 and 3 are isostructural and consist of neutral chains with triazolopyrimidine bridging ligands through N1, N3 nitrogen atoms. Compound 4 exhibits a 2D rectangular-grid-like structure and complexes 7 and 8 are cyanate-bridged chains formed by defective cubanes. Magnetic and luminescent properties of these materials have also been studied.

Silver(I) coordination complexes with the versatile and biomimetic ligands 1,2,4-triazolo[1,5-a]pyrimidine (tp), 5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine (dmtp) and 7-amine-1,2,4-triazolo[1,5-a]pyrimidine (7atp) all feature dinuclear [Ag₂(μ-tp)₂]²⁺ building units (where tp is a triazolopyrimidine derivative), which are the preferred motif, independently of the counter-anion used. According to AIM (atoms in molecules) and ELF (electron localization function) analyses, this fact is due to the great stability of these dinuclear species. The complexes structures range from the dinuclear entities [Ag₂(μ-tp)₂(CH₃CN)₄](BF₄)₂ (1), [Ag₂(μ-tp)₂(CH₃CN)₄](ClO₄)₂ (2), [Ag₂(μ-7atp)₂](ClO₄)₂ (3) and [Ag₂(μ-dmtp)₂(CH₃CN)](PF₆)(ClO₄) (4) over the 1D polymer chain [Ag₂(μ-CF₃SO₃)₂(μ-dmtp)₂]_n (5) to the 3D net {[Ag₂(μ₃-tp)₂](PF₆)₂· ∼6H₂O}_n (6) with NbO topology.