70. Gibbons, S. K.; Hughes, R. P.; Glueck, D. S.; Royappa, A. T.; Rheingold, A. L.; Arthur, R. B.; Nicholas, A. D.; Patterson, H. H. Inorg. Chem. 2017, 56, 12809–12820. Synthesis, Structure, and Luminescence of Copper(I) Halide Complexes of Chiral Bis(phosphines).

Abstract

For investigation of structure-property relationships in copper phosphine halide complexes, treatment of Cu(I) halides with chiral bis(phosphines) gave dinuclear [Cu((R,R)-i-Pr-DuPhos)(µ-X)]₂ (X = I, Br, Cl; 1-3), [Cu(µ-((R,R)-Me-FerroLANE)(µ-I)]₂ (5), [Cu((S,S)-Et-FerroTANE)(I)]₂ (6), pentanuclear cluster Cu₅I₅((S,S)-Et-FerroTANE)₃ (7), and the monomeric Josiphos complexes Cu((R,S)-CyPF-t-Bu)(I) (8) and Cu((R,S)-PPF-t-Bu)(I) (9); 1-3, 5 and 7-9 were structurally characterized by X-ray crystallography.  Treatment of iodide 1 with AgF gave [Cu((R,R)-i-Pr-DuPhos)(µ-F)]₂ (4). DuPhos complexes 1-4 emitted yellow-green light on UV irradiation at room temperature in the solid state.  This process was studied by low-temperature emission spectroscopy and by DFT calculations, which assigned the luminescence to (M+X)LCT (Cu₂X₂ to DuPhos aryl) excited states.  Including Grimme’s dispersion corrections in the DFT calculations (B3LYP-D3) gave significantly shorter Cu-Cu distances than those obtained using B3LYP, with the non-dispersion corrected calculations better matching crystallographic data; other intramolecular metrics are better reproduced using B3LYP-D3. Discussion of factors leading to this unusual observation is presented.