Exploring the Self-Assembled Tacticity in Aurophilic Polymeric Arrangements of Diphosphanegold(I) Fluorothiolates

Despite the recurrence of aurophilic interactions in the solid-state structures of gold(I) compounds, its rational control, modulation, and application in the generation of functional supramolecular structures is an area that requires further development. The ligand effects over the aurophilic-based supramolecular structures need to be better understood. This paper presents the supramolecular structural diversity of a series of new 1,3-bis(diphenylphosphane)propane (dppp) gold(I) fluorinated thiolates with the general formula [Au₂(SR_F)₂(μ-dppp)] (SR_F = SC₆F₅ (1); SC₆HF₄-4 (2); SC₆H₃(CF₃)₂-3,5 (3); SC₆H₄CF₃-2 (4); SC₆H₄CF₃-4 (5); SC₆H₃F₂-3,4 (6); SC₆H₃F₂-3,5 (7); SC₆H₄F-2 (8); SC₆H₄F-3 (9); SC₆H₄F-4 (10)). These compounds were synthesized and characterized, and six of their solid-state crystalline structures were determined using single-crystal X-ray diffraction. In the crystalline arrangement, they form aurophilic-bridged polymers. In these systems, the changes in the fluorination patterns of the thiolate ligands tune the aurophilic-induced self-assembly of the compounds causing tacticity and chiral differentiation of the monomers. This is an example of the use of ligand effects on the tune of the supramolecular association of gold complexes.