Metastable Adducts as a Route to Silver Thiolate Processing on the Way to New Thiorenes: Structural, Spectroscopy, and Computational Data.

Abstract

Metal-organic chalcogenides (MOCs) represent an emerging class of organic-inorganic compounds that exhibit remarkable semiconductor and luminescent properties that can be finely tuned by varying the organic ligands. In this work, we investigate previously unreported polymeric silver thiolates, [Ag(S-ArF)]n (where ArF = a polyfluorinated aryl group). We demonstrate that the recrystallization of these compounds from pyridine and its derivatives (py-R) affords crystalline 1D coordination polymers (CPs) based on [(py-R)Ag(S-ArF)]n chains. Through this approach, we prepared 17 novel complexes, which were structurally characterized by single-crystal X-ray diffraction (SCXRD). A majority of these complexes (14 of 17) are infinite, ribbon-like polymers formed by the lateral association of two [(py-R)Ag(S-ArF)]n chains. These structures predominantly feature argentophilic interactions ranging from infinite Ag···Ag chains to isolated dimers. Furthermore, quantum chemical calculations predict semiconducting behavior for these materials. Notably, bulk [(py-R)Ag(S-ArF)]n MOCs slowly lose their coordinated pyridine molecules, yielding polymeric [Ag(S-ArF)]n that adopts a 2D structure analogous to the [Ag(S-Ph)]n ("thiorene") network. Finally, the practical utility of the prepared complexes is demonstrated in the design of novel photoluminescent coatings based on [Ag(S-ArF)]n thin films.

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