A flexible bidentate cyclic phosphine, namely, 1,5-bis(p-tolyl)-3,7-bis(pyridin-2-yl)-1,5-diaza-3,7-diphosphacyclooctane (PNNP), was used as a template to construct a family of binuclear heteroleptic phosphine alkynyl complexes [PNNP(AuC2R)2], with R = Ph, C6H10OH, C5H8OH, (CH3)2COH, Ph2COH. All complexes obtained were characterized by CHN elemental analysis, NMR spectroscopy, and single-crystal X-ray analysis. It was found that the gold(I) complexes demonstrate a different organization of the crystal structure depending on the nature of the cocrystallized solvent (dichloromethane, acetone, and acetonitrile) because of formation of the supramolecular complexes through hydrogen bonding. These weak interactions appear to determine the conformation, packing, and spatial cooperation of flexible complex molecules that are reflected in the photophysical properties, which were carefully investigated in solution and in the solid state. The complexes demonstrate weak emission in solution at room temperature, and freezing results in blue shifting of the emission, which is accompanied by a significant increase in the luminescence intensity. Being isolated from dichloromethane, all gold(I) complexes exhibit green phosphorescence in the solid state, and the complexes with R = Ph and Ph2COH display substantial variation of their emission color after recrystallization from acetone and acetonitrile, respectively, which manifests itself as a significant bathochromic shift of up to 120 nm. The structural nonrigidity of the gold(I) complexes obtained and its impact on the properties of low-energy excited states were investigated in detail by density functional theory calculations, which indicate the significant role of the structural flexibility of the PNNP ligand in the formation of the low-energy excited states and confirm the impact of rotation of the functional groups in the coordination sphere on the emission properties of complexes.