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A series of d10 coinage metal thiosalicylate coordination polymers (CPs) is reported. The 1D structures of the three CPs are formed by M3S3 fused hexagons for Cu and Ag compounds and interpenetrated helical chains for Au CP. Depending on the metal, solid‐state red and NIR emissive CPs are obtained with quantum yields up to 50 %, providing a great opportunity to replace the actual emissive critical raw materials. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Solventless synthesis and processing of Metal Organic Frameworks (MOFs) is critical to implement these materials in applied technologies. Vapour phase synthesis of MOF thin films is particularly suitable for such applications, but challenging compared to the conventional solution based methods. It is therefore compelling to advance and widen the vapour phase synthesis of MOF thin films. Crystalline copper terephthalate MOF thin films are grown in the vapour phase by means of atomic and molecular layer deposition (ALD/MLD) on different kinds of substrates. Expanding from the pioneering work, the formation of the 3D phase is clearly evidenced for the first time and the adaptability of the process to several kinds of substrates is revealed. A directional film growth is observed at the early stage of the ALD/MLD process leading to oriented MOF crystallites on a surface, when isotropical growth proceeds with the increasing number of ALD/MLD cycles. Notably, this study primarily demonstrates a heteroepitaxial growth achievable in the vapour phase by using DMOF-1 single crystals as the starting surface with a lattice matching topology. Such an approach offers an appealing pathway to develop MOF on MOF superlattice materials in the vapour phase.

The discovery of a universal memory that exhibits fast access speed, high-density storage, and non-volatility has fuelled research into phase-change materials over the past decades. In spite of the efficiency of the inorganic chalcogenides for phase-change random access memory (PCRAM), they still have some inherent drawbacks, such as high temperature required for phase change and difficulty to control the domain size of the phase change, because of their brittleness. Here we present a Au I -thiolate coordination polymer which undergoes two successive phase changes on application of mild heating (<200 °C) from amorphous-to-crystalline1-to-crystalline2 phases. These transitions are reversible upon soft hand grinding. More importantly, each phase exhibits different photoluminescent properties for an efficient optical read-out. We believe that the ability of the Au I -thiolate coordination polymer to have reversible phase changes under soft conditions and at the same time to display distinct optical signals, can pave the way for the next generation of PCRAM., (© 2022 Wiley-VCH GmbH.)

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 -SPhCO 2 H)] n . Its structure is lamellar with an inorganic layer made of Au-S-Au-S helical chains, similar to the [Au( p -SPhCO 2 H)] 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 -SPhCO 2 H)] 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., Competing Interests: The authors declare no conflicts of interest.