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

Abstract

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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)] (1) and {[CuI(nic)]·ACN} (2), one tetrameric cubane [CuI(3-phpy)] (3), one rhomboid dimer [CuI(8-ClQuin)] (4) and one monomer [CuI(1-CHisoQuin)] (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.