Structure directing factors and photophysical properties of five Cu(I)-iodide materials with N-donor heteroaromatic ligands

In this work, two families of Cu(I)-iodide complexes with N-heterocyclic donors ligands bearing amide, phenyl, chloro, and methyl substituents have been synthesized to combine two structural directing factors: attractive interactions and steric bulkiness. To this aim, we synthesized five Cu(I)-iodide based complexes: two 1D coordination polymers [CuI(isn)]n (1) and {[CuI(nic)]·ACN}n (2), one tetrameric cubane [CuI(3-phpy)]4 (3), one rhomboid dimer [CuI(8-ClQuin)]2 (4) and one monomer [CuI(1-CH3isoQuin)] (5). Interestingly, easy ligand dissociation and marked distortions within the molecular structure enabled structural rearrangements between the mentioned arrays. Then, we compiled the structures contained in this family of materials and provided a shape map and a conversion pathway between the most similar arrays, the cubane and the staircase polymer. Finally, the photophysical properties of 1–5 were investigated and electronic transitions were identified and supported by DFT and TD-DFT calculations since their photophysical properties are strongly dependent on the molecular arrangement and electronic distribution.