A New Lamellar Gold Thiolate Coordination Polymer, [Au(m-SPhCO2H)]n, for the Formation of Luminescent Polymer Composites

Abstract

The photoluminescence of gold thiolate clusters brings about many potential applications, but its origin is still elusive because of its complexity. A strategy in understanding the structure–properties relationship is to study closely related neutral gold thiolate coordination polymers (CPs). Here, a new CP is reported, [Au(m-SPhCO2H)]n. Its structure is lamellar with an inorganic layer made of Au–S–Au–S helical chains, similar to the [Au(p-SPhCO2H)]n analog. An in-depth study of its photophysical properties revealed that it is a bright yellow phosphorescent emitter with a band centered at 615 nm and a quantum yield (QY) of 19% at room temperature and in a solid state. More importantly, a comparison to the para-analog, which has a weak emission, displayed a strong effect of the position of the electron withdrawing group (EWG) on the luminescent properties. In addition, [Au(m-SPhCO2H)]n CPs were mixed with organic polymers to generate transparent and flexible luminescent thin films. The ability to tune the emission position with the appropriate contents makes these nontoxic polymer composites promising materials for lighting devices.

Supramolecular Gold Chemistry: From Atomically Precise Thiolate-Protected Gold Nanoclusters to Gold-Thiolate Nanostructures

“…The aim of this Special Issue on "Supramolecular Gold Chemistry" was to provide a unique international forum aimed at covering a broad description of results involving the supramolecular chemistry of gold with a special focus on the gold-sulfur interface leading to hybrid materials, ranging from gold-thiolate complexes, [3] to thiolate-protected gold nanoclusters [4][5][6][7][8][9][10][11] and gold-thiolate supramolecular assemblies or nanoparticles. [12][13][14] The role of thiolates on the structure and optical features of gold nanohybrid systems (ranging from plasmonic gold nanoparticles and fluorescent gold nanoclusters to self-assembled Au-containing thiolated coordination polymers) has been highlighted in the review article by Csapó and coworkers [14].…”

“…Theoretical investigations are also useful for structural characterization. Cheng and coworkers theoretically investigate Au 70 S 20 (PPh 3 ) 12 using density functional theory calculations. The electronic and geometric structure of Au 70 S 20 (PPh 3 ) 12 is further addressed based on the popular divide and protect concept and the superatom network model [7].…”

“…Jin and coworkers highlight this molecular-like behavior by thoroughly exploring the differences in the photophysical properties of small organic molecules, gold-thiolate complexes, nanoclusters, and metallic-state nanoparticles [8]. The luminescence properties of 6-aza-2-thio-thymine stabilized gold nanoclusters [9] and gold thiolate coordination polymers [12] demonstrate the high potential of such nanomaterials for bio-sensing or lighting devices. However, in such nanosystems, the origin of photoluminescence (PL) is still not fully understood.…”

Coordination-Driven Self-Assembly on Polymer Surfaces for Efficient Synthesis of [Au(SPh)]n Coordination Polymer-Based Films

“…After the formation of the [Au­(SPh)] n CPs on the nylon film, this nylon emission decreased. This is because the formation of CPs on the nylon substrate lead to an interruption of excitation irradiation and emission from the nylon . Another characteristic peak around 680 nm appeared and was consistent with that of [Au­(SPh)] n CPs prepared by the conventional hydrothermal approach.…”

Sustainable and Efficient Low‐Energy Light Emitters: A Series of One‐Dimensional d10 Coinage Metal–Organic Chalcogenolates, [M(o‐SPhCO2H)]n

“…It has also a 2D Au(I)‐S network associated with a yellow emission and a QY of 19 % in solid state at room temperature. It was mixed with organic polymers to generate transparent and flexible luminescent thin films [8] …”