The synthesis, structural and photophysical characterization, and theoretical study of tetranuclear copper(i) cubane-type Cu4I4 clusters with different 10-(aryl)phenoxarsine ligands are presented.

Luminescent As-supported Cu4I4 cubane tetramers with a dual band emission, showing temperature-dependent intensities, were synthesized and studied in detail by DFT calculations.

Synthesis and structural and photophysical characterization of platinum dihalogenide complexes formulated as [PtHal2L2], where Hal = Cl and I, with different 10-(aryl)­phenoxarsine ligands such as 10-(p-chlorophenyl)­phenoxarsine, 10-(p-tolyl)­phenoxarsine, and 10-(phenyl)­phenoxarsine are reported. The structures of complexes were determined by NMR spectroscopy, mass spectrometry, and X-ray analysis. Cis/trans isomerism of the complexes in solution was studied by NMR spectroscopy. In the solid state, under UV irradiation, platinum diiodide trans complexes exhibit an intense orange-red emission, which was attributed to a metal halide-centered triplet state. The UV/vis absorption and emission properties were studied and rationalized by density functional theory (DFT) and time-dependent DFT calculations.

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Dinuclear complexes of the composition Cu2I2L2Py2 and Cu2I2L4 are obtained by the reaction of 10‐(aryl)phenoxarsine ligands (L) with copper iodide in pyridine or non‐coordinated solvent. Unexpectedly the 1D polymeric complex [Cu2I2L4]n is formed as the only product by the reaction of 10‐(p‐ethoxyphenyl)phenoxarsine with CuI in the molar ratio 1 : 2. All complexes and the initial phenoxarsine ligands are fully characterized by elemental analysis, NMR‐ and IR spectroscopy. X‐ray structure is determined for eight complexes and five ligands. In the 1D coordination polymer [Cu2I2L4]n copper atoms are in zigzag‐like chain arrangement demonstrating the first example of such Cu‐I−Cu‐I binding. The empirical Tolman cone angles for 10‐(aryl)phenoxarsine ligands in complexes are calculated to lie in the range of 125–152°. The dependence of the Tolman angle values on the position of aryl substituent at arsenic atom is demonstrated.