A series of novel luminescent neutral cyclometalated gold (III) complexes of the type cis-(N(boolean AND)C)Au(C CR)(2)] (R = aryl silyl groups) having different cyclometalating cores (N(boolean AND)C) have been synthesized by CuI promoted halide to alkynyl metathesis with NEt(3) as in situ deprotonating agent. Along with spectroscopic characterizations (nudear magnetic resonance and infrared spectroscopies and electrospray ionization mass spectrometry) and elemental analysis, the molecular structures of some of the complexes have been established by single-crystal X-ray diffraction studies. Photophysical studies reveal that the complexes exhibit room-temperature phosphorescence (RTP). Experimental observations and density functional theory calculations qualitatively suggest limited participation of the metal and allcynyl ligands in the lowest energy emitting state. The nature of the emission is mainly governed by metal-perturbed (3)IL(pi-pi*) transitions originating from the cyclometalate part of the molecule, and its variation readily leads to the tuning of the emission wavelengths. Cyclic voltammetry measurements of selected complexes showed irreversible redox behavior with nearequivalent cathodic peak potential (E(p,c)) assigned to the C(boolean AND)N core.