Abstract

Two new Ag(I) complexes (1 and 2) with pyrimidine ligands were synthesized, and their single crystals were grown using the slow evaporation method. The study explores the synergistic role of hydrogen bonding and CH?? interactions in the supramolecular assembly of these pyrimidine complexes, integrating insights from single-crystal X-ray crystallography and Density Functional Theory (DFT) calculations. In both complexes, each Ag(I) ion is coordinated to three nitrogen atoms, forming a wavy 1D coordination polymer supported by hydrogen bonds and CH?? interactions. Additionally, the complexes exhibit an intricate hydrogen-bonding network involving lattice perchlorate anions, which connects the units into a 2D supramolecular polymer with cavities. The 2D conformational differences in the crystalline state are influenced by the dihedral angles between the planes of Ag-bridged pyrimidine ring and the tolyl/methoxyphenyl rings, resulting from the presence of methyl/methoxy functional groups in the ligands. DFT analysis provided a deeper understanding of the self-assembly mechanisms in the solid-state structures of the complexes, supporting experimental results. Moreover, DFT results imply that the coordination polymers formed by these complexes should have pronounced thermodynamic stability and could be active in redox reactions acting as good electron acceptors. © 2025 Elsevier B.V.