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.
Highlights
Gold(I) coordination chemistry is intrinsically conjoined to supramolecular chemistry by the aurophilic interactions [1,2,3]
The distortions observed from the linearity expected for the P–Au–S moiety are mainly due to the formation of the Au–Au contacts; no correlation exists between the aurophilic distance and the Au–S/P
Compounds 4, 9, and 10 crystallize in the triclinic P−1 spatial group; in the three cases, two molecular units are related by the inversion center per unit cell and the aurophilic polymers containing these units grow parallel to the a crystallographic axis in opposite directions from the other
Summary
Gold(I) coordination chemistry is intrinsically conjoined to supramolecular chemistry by the aurophilic interactions [1,2,3] These counterintuitive interactions, which have attracted attention since the beginning of the twenty-first century, are still a subject of interest due to the potential applicability of supramolecular gold assemblies in the production of materials including, for example, luminescent materials, gelators, and liquid crystals [4,5,6,7]. In this quest, one of the main challenges is the rational control of the aurophilic contact and its supramolecular consequences [8,9,10,11,12].
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