Design of luminescent complexes with different Cu4I4 cores based on pyridyl phenoxarsines

Abstract

A series of luminescent Cu₄I₄ clusters with stair-step, cubane, and octahedral geometries supported by a novel type of cyclic As,N-ligand, pyridyl-containing 10-phenoxarsines, were synthesized and characterized by NMR spectroscopy, mass spectrometry, elemental analysis, and single-crystal X-ray diffraction analysis. An unusual arrangement of As,N-bidentate and μ²-iodo ligands was found in the octahedral cluster. The structural diversity of the Cu(I) complexes is reflected in their photophysical properties: the phosphorescence spectra of the compounds display emission in a broad spectral range of 495–597 nm. The complex with the Cu₄I₄L₂ stoichiometry bearing a stair-step Cu₄I₄ core demonstrates temperature-dependent dual emission. The luminescence properties of all complexes were rationalized by DFT calculations.