Shedding light on an ultra-bright photoluminescent lamellar gold thiolate coordination polymer [Au(p-SPhCO₂Me)]_n

Abstract

The first structure elucidation of a lamellar gold thiolate coordination polymer is described. [Au(p-SPhCO2Me)]n is obtained from the simultaneous esterification of mercaptobenzoic acid and reduction of the Au(iii) precursor. Despite the presence of aurophilic interactions, the intense phosphorescence (QY ∼ 70%) originates from intra-ligand and metal-to-ligand transitions.

Manipulation of Inorganic Atomic‐Layer Networks by Solution‐Phase Co‐assembly

“…ATCP nanosheets have well‐resolved sharp UV/Vis absorption peaks, which are suggested to result from ligand‐to‐metal charge‐transfer (LMCT) and metal‐centred charge‐transfer (MCCT) transitions ,,. The absorption peaks can be an indication of the formation of nanosheets.…”

“…There is one report on resolving the in‐plane structure of Ag I –alkane thiolates with PXRD, which proposes that S is three‐coordinate, and later this model was questioned by other studies . In 2016, a detailed crystal structure of [Au I ‐ p ‐SPhCO 2 Me] n was resolved, which suggests that S is two‐coordinate . For other ATCP lamellae, the in‐plane structures are still not clear.…”

“…[15] With properl igands, the linearly coordinated metal-thiolate CPs can self-assemble into 2D lamellar structures. [16] Studies have revealed that the single-layer structure in the lamellae is composed of a slab of metal-S network in the centre with the substituent groupso ns ulfur pointing up andd own from the network (Figure 1a). [16] In contrastt om ostC Ps, which utilize O-or N-containingf unctional groups as donors to form coordination networks, the metal-S networks are formed through interatomic interactions, such as coordination bonds between metal ions and Sa toms, as well as metallophilic interactions among noble metali ons (Figure 1b).…”

“…[16] Studies have revealed that the single-layer structure in the lamellae is composed of a slab of metal-S network in the centre with the substituent groupso ns ulfur pointing up andd own from the network (Figure 1a). [16] In contrastt om ostC Ps, which utilize O-or N-containingf unctional groups as donors to form coordination networks, the metal-S networks are formed through interatomic interactions, such as coordination bonds between metal ions and Sa toms, as well as metallophilic interactions among noble metali ons (Figure 1b). The metal-S network is soft andv ulnerable to the environment, [16f] and therefore it is possible to modulate the metal-S network by changingt he substituent on St hroughm ultiligand co-assembly.A lthough as eries of metal-thiolatel amellar CP structures have been prepared with different thiol ligands, no such attempt has been made.…”

Self‐Templated Assembly of AuI/AgI‐Thiolate Sheets with Central Holes

“…Pattern index of the XRD data indicates the crystals have either orthorhombic or monoclinic unit cell strucure. Taking consideration of the zig‐zag conformation of lamellar Au I ‐thiolate and Ag I ‐thiolate, the coordination polymer chains are suggested to pack side‐by‐side with these metallo‐interactions as shown in Figure b. However, the strucutre details can not be infered with XRD because of the less resolved diffraction peaks.…”