RyotoI naba, [a] Ikuo Kawashima, [a] To shiki Fujii, [a] Ta kashiY umura, [b] HiroakiI moto,* [a, c] and Kensuke Naka* [a, c]

Tetranuclear cubic copper(I) iodide (CuI) complexes were synthesized by utilizing tertiary arsine ligands such as triphenylarsine, tri(p-tolyl)arsine, 9-phenyl-9-arsafluorene, and 1-phenylarsolane; except for triphenylarsine, these ligands were prepared by the practical methods that we previously developed. The obtained complexes exhibited intense emission in the crystalline states even at room temperature. Their emission colors were drastically changed by mechanical stimulus, temperature, and excitation wavelength. These complexes are the first examples of cubic Cu4I4 complexes with arsenic ligands exhibiting stimuli-responsive and excitation wavelength-dependent luminescence.

Heteroatom-fused π-conjugated molecules have attracted considerable attention, and various elements for such fusion have been investigated. Herein, we focused on pnictogen-fused heterofluorenes. The structures, reactivity with O2 and I2, coordination ability to AuCl, and photophysical properties were systematically studied to better understand the effects of pnictogen atoms on the nature of π-conjugated molecules.

Tertiary arsenic ligands were utilized for the Stille coupling reaction to elucidate the relationship between ligand structure and catalytic activity. Tri(p-anisyl)arsine showed the highest yield, and the mechanism was analysed by DFT calculations.

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