Synthesis and Characterization. Chiral binuclear NHC Au(I) complexes 1-R and 1-S were synthesized in 72-75% yields through the reaction of {1,3-bis[(R)-1-phenylethyl]-imidazol-2-yl} Au(I) chloride or {1,3-bis[(S)-1-phenylethyl]-imidazol-2-yl} Au(I) chloride with 1,4-benzenediboronic acid bis(pinacol) ester in toluene at 70°C in presence of potassium hydroxide as a base (Scheme 1). The deuterated analogs of 1-R (1-R-d4 and 1-R-d20) used in solid-state NMR studies were obtained by the same method from the deuterated precursors (See Section S2, Supporting Information). The complexes were characterized using 1 H and 13 C NMR spectroscopy, high-resolution massspectrometry, C, H, and N elemental analysis, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), variable temperature (VT) single-crystal and powder X-ray diffraction (SCXRD and PXRD), circular dichroism (CD), photoluminescence, and circularly polarized luminescence (CPL) spectroscopies. through n-hexane vapor diffusion into dichloromethane/ethyl acetate solution and yielded crystalline samples with no solvent inclusion, as confirmed by TGA and elemental analysis. The obtained single crystals were characterized by SCXRD, while the composition of the bulk crystalline samples was confirmed by PXRD at room temperature and elemental analysis. The crystal structures of the complexes are depicted in Figures and, the crystallographic data parameters are given in Tables , while the geometrical parameters are listed in Table in the Supporting Information.