Synthesis and Photophysical Properties of T‐Shaped Coinage‐Metal Complexes

The photophysical properties of a series of T‐shaped coinage d10 metal complexes, supported by a bis(mesoionic carbene)carbazolide (CNC) pincer ligand, are explored. The series includes a rare new example of a tridentate T‐shaped AgI complex. Post‐complexation modification of the AuI complex provides access to a linear cationic AuI complex following ligand alkylation, or the first example of a cationic square planar AuIII−F complex from electrophilic attack on the metal centre. Emissions ranging from blue (CuI) to orange (AgI) are obtained, with variable contributions of thermally‐dependent fluorescence and phosphorescence to the observed photoluminescence. Green emissions are observed for all three gold complexes (neutral T‐shaped AuI, cationic linear AuI and square planar cationic AuIII). The higher quantum yield and longer decay lifetime of the linear gold(I) complex are indicative of increased phosphorescence contribution. T‐Shaped coinage‐metal complexes: Photoluminescence tuning mediated by a bis(mesoionic carbene)amido pincer ligand for d10 complexes of unusual T‐shape, linear AuI and square planar AuIII.