Hsu, Ying-FengYing-FengHsuCheng, Shih-YingShih-YingChengCheng, Che-AnChe-AnChengKang, Yu-HsuanYu-HsuanKangLiu, Yi-HungYi-HungLiuKong, Kien VoonKien VoonKongYang, Jye-ShaneJye-ShaneYang2025-10-302025-10-302025https://scholars.lib.ntu.edu.tw/handle/123456789/733283We report two stimuli-responsive luminescent assemblies based on homoleptic alkynyl gold(I) clusters, [(AuC≡CR)n], where R is a pentiptycene unit and n = 4 or 6. The green-emissive form (1Gs) adopts a vortex-like arrangement and exhibits photochromic luminescence, shifting from green to yellow to orange. In contrast, the yellow-emissive form (1Ys) adopts a less rigid structure, likely a radial arrangement, and displays thermochromic luminescence, transitioning from yellow to orange to red. These divergent behaviors arise from structural differences in η2-Au bonding, which modulate supramolecular geometry, pentiptycene–pentiptycene packing, and the strength of Au…Au interactions, thereby governing excited state aurophilicity. This work demonstrates the first luminochromic [(AuC≡CR)n] system and introduces a design strategy that leverages pentiptycene scaffolds to regulate excited-state aurophilicity for photo- and thermoresponsive luminescence.en[SDGs]SDG3journal article10.1039/d5dt02075a