Synthesis, Crystal Structure, Theoretical Study, and Luminescence Spectroscopy of A W/Cu/S Cluster with 1, 10‐Phenanthroline

The reaction of [NH 4 ] 2 WOS 3 with Cu(CH 3 CN) 4 ClO 4 and 1, 10‐phenanthroline(phen) in CH 2 Cl 2 afforded the butterfly‐shaped cluster {[WOS 3 Cu 2 (phen) 2 ] · CH 2 Cl 2 } ( 1 ), which was characterized by elemental analysis, single‐crystal X‐ray diffraction as well as IR and fluorescence spectroscopy. The complex crystallizes in the triclinic system with space group P $\bar{1}$ [ a = 8.3976(17) Å, b = 9.6771(19) Å, c = 18.460(4) Å, α = 89.94(3)°, β = 80.33(3)°, γ = 70.38(3)°, V = 1390.5(5) Å 3 , and Z = 2]. Single crystal X‐ray diffraction analysis reveals that complex 1 displays pairwise π–π stacking. Density functional theory and time‐dependent density functional theory calculations at the B3LYP/LanL2DZf+6‐31G* level were performed on complex 1 to rationalize its experimental absorption spectra. Fluorescence spectroscopy reveals that complex 1 exhibits luminescence in EtOH solution at room temperature.