Metal-free and metal-containing molecular trefoil knots are fascinating ensembles that are usually covalently assembled, the latter requiring the rational design of di-or multidentate/multipodal ligands as connectors. In this work, we describe the self-assembly of pentadecanuclear Au I trefoil knots [Au 15 (C�CR) 15 ] from monoalkynes HC�CR (R = 9,9-X 2 -fluorenyl with X = nBu, n-hexyl) and [Au I (THT)Cl]. Hetero-bimetallic counterparts [Au 9 M 6 (C�CR) 15 ] (M = Cu/Ag) were selfassembled by reactions of [Au 15 (C�CR) 15 ] with [Cu-(MeCN) 4 ] + /AgNO 3 and HC�CR. The type of pentadecanuclear trefoil knots described herein is characterized by X-ray crystallography, 2D NMR and HR-ESI-MS.[Au 9 Cu 6 (C�CR) 15 ] is relatively stable in hexane; its excited state properties were investigated. DFT calculations revealed that non-covalent metal-metal and metal-ligand interactions, together with longer alkyl chain-strengthened inter-ligand dispersion interactions, govern the stability of the trefoil knot structures.