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

Abstract

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(SRF)2(μ-dppp)] (SRF = 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.

Fluorination Effects in XPhos Gold(I) Fluorothiolates

“…Solvents were obtained from JT Baker (Thermo Fisher Scientific, Waltham, MA, USA) and used without previous treatment. Pb(SRF) 2 and AgSCF 3 were prepared as previously reported [46,47].…”

Directing the Crystal Packing in Triphenylphosphine Gold(I) Thiolates by Ligand Fluorination

“…Lead thiolates Pb(SR F ) 2 used in the synthesis of the compounds examined herein were obtained by the reaction of stoichiometrical amounts of aqueous lead acetate (Pb(CH 3 COO) 2 ) with a concentrated solution of the corresponding thiol in methanol, yielding a yellow or white (SR F = SC 6 HF 4 , SCH 2 CF 3 ) solid that was thoroughly washed with water and hexane. 61 Silver(I) trifluoromethylthiolate, obtained as described in ref 62, was used in the synthesis of 12 because of the instability of the lead analogue. The compound [AuCl(PPh 3 )] was obtained by the direct reaction of K[AuCl 4 ] with PPh 3 as reported by Fackler et al 63 The synthesis and characterization of compounds 1, 3, 11, and 12 were previously reported.…”