Self‐Assembly of a Au 16 Ring via Metal–Metal Bonding Interactions

Metal–metal bonding interactions have been employed as an efficient strategy to generate a number of unique gold(I) metallo‐macrocycles with fascinating functions. The self‐assembly, crystal structure and emission property of novel nest‐like tetramer 1 4 , namely, {[Au 4 (μ‐dppm) 2 (μ‐dctp 2− )](BF 4 ) 2 } 4 ⋅ (CH 3 CN) 2 (dppm=bis(diphenylphosphino)methane, dctp 2− = N , N ′‐bis(dicarbodithioate)‐2,11‐diaza[3.3]paracyclophane) is reported. The complex has been characterized by single‐crystal X‐ray diffraction analysis, 1 H NMR spectroscopy, 13 C NMR spectroscopy, and CSI‐MS spectrometry. The aggregate demonstrates the sixteen gold(I) atoms are arranged in a ring with a circumference of 50.011(68) Å generated by Au I ⋅⋅⋅Au I attractions. UV/visible and luminescence spectroscopy revealed that this Au I ⋅⋅⋅Au I bonded metallo‐macrocycle exhibited yellow phosphorescence.