The alkyne unit of 4′-ethynyl-2,2′:6′,2″-terpyridine has been functionalized with Ph 3PAu, (2-tolyl) 3PAu or Au(dppe)Au units to produce compounds 1– 3, respectively. These derivatives have been characterized by electrospray mass spectrometry, solution 1H and 13C NMR, UV–Vis and emission spectroscopies, and single crystal X-ray diffraction. In the solid state, molecules of 1 or 2 pack with separated domains of tpy and R 3PAu units; the tpy units in 2 (but not 1) exhibit face-to-face π-stacking. Compound 3 crystallizes as 2( 3) . CHCl 3, and the folded conformation of the dppe backbone results in a short (2.9470(8) Å) aurophilic interaction. Folded molecule 3 captures CHCl 3, preventing intramolecular face-to-face π-interactions between the tpy units. In CH 2Cl 2 solution, 1– 3 are emissive when excited between 230 and 300 nm, but over minutes when λ ex = 230 nm, the emission bands decay as the compounds photodegrade.