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The synthesis of linear symmetric ethynyl‐ and acetylide‐amidinates of the coinage metals is presented. Starting with the desilylation of the complexes [{Me 3 SiC≡CC(NDipp) 2 } 2 M 2 ] (Dipp=2,6‐diisopropylphenyl) (M=Cu, Au) it is demonstrated that this compound class is suitable to serve as a versatile metalloligand. Deprotonation with  n ‐butyllithium and subsequent salt metathesis reactions yield symmetric tetranuclear gold(I) acetylide complexes of the form [{(PPh 3 )AuC≡CC(NDipp) 2 } 2 M 2 ] (M=Cu, Au). The corresponding Ag complex [{(PPh 3 )AuC≡CC(NDipp) 2 } 2 Ag 2 ] was obtained by a different route via metal rearrangement. All compounds show bright blue or blue‐green microsecond long phosphorescence in the solid state, hence their photophysical properties were thoroughly investigated in a temperature range of 20–295 K. Emission quantum yields of up to 41 % at room temperature were determined. Furthermore, similar emissions with quantum yields of 15 % were observed for the two most brightly luminescent complexes in thf solution.

Efficient Blue Phosphorescence in Gold(I)‐Acetylide Functionalized Coinage Metal Bis(amidinate) Complexes