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.