Pyridinyl carbohydrazone ligands with different positions between functional groups of – NNHC(O) – and N py ( ortho -, meta - and para -) have been applied for the synthesis of cuprous halide complexes. X-ray crys- tallography reveals that the ortho analogous ligand, L o , functions in a chelating mode, adopting a mononu- clear structure in complex C o , [CuClL o PPh 3 ], while the meta and para analogs, L m and L p , act as ambidentate ligands, coordinating through the N py atom in halogen-bridged binuclear complexes [Cu( μ - X)LPPh 3 ] 2 (X = Cl, Br, I and L = L m , L p ). The influence of non-covalent intermolecular interactions on the as- sembly of the final structures has been discussed by geometrical and Hirshfeld analyses. Moreover, the photophysical properties of the complexes have been explored, both experimentally and theoretically. The influence of ligand structure and halide variations on the structural and photophysical aspects of the com- plexes has been considered in this study.
