LAUSR

Abstract Self-assembly of cuprous iodide [Cu(I)] and five flexible bis(pyridyl) ligands generates five complexes, [CuI(L1)(PPh3)]2·2H2O (1), [Cu2I2(L2)(PPh3)2]n·2nCH2Cl2 (2), [CuI2(L3)] (3), [Cu3I3(r-L1)]n (4) and [Cu3I3(r-L2)]n·nH2O (5) (PPh3 = triphenylphosphine, L1 = N,N′-bis(pyridin-4-ylmethylene)propane-1,3-diamine, L2 = N,N′-bis(pyridin-3-ylmethylene)propane-1,3-diamine, L3 = N,N′-bis(pyridin-2-ylmethylene)propane-1,3-diamine, r-L1 = N,N′-bis(pyridin-4-ylmethyl)propane-1,3-diamine, r-L2 = N,N′-bis (pyridin-3-ylmethyl)propane-1,3-diamine), which have been characterized by elemental analysis, IR, TG, PL, powder and single-crystal X-ray diffraction. Owing to the terminal coordination of PPh3 molecules, complexes 1 and 2 only present [Cu2I2] cluster based dinuclear and chain structures. The in situ oxidized Cu(II) cation in complex 3 is triply coordinated by both the pyridyl N and aliphatic N atoms, thus forming mononuclear motif. In contrast, r-L1 and r-L2 ligands in complexes 4 and 5 join adjacent [Cu6I6] clusters with all the N atoms coordinating to the Cu(I) cations, giving rise to pcu net and layer structure. The structural diversities of complexes 1–5 can be attributed to the coordination modes and conformations of the five ligands as well as the size of [CuI]n clusters. Moreover, room temperature solid-state luminescent properties demonstrate that complexes 1 and 5 exhibit stronger yellow and blue emission at 592 and 489 nm.