Thiolate Coordination Polymer Research Articles

Gold(I)-Thiolate Coordination Polymers as Multifunctional Materials: The Case of Au(I)-p-Fluorothiophenolate.

Gold-sulfur interaction has vital importance in nanotechnologies and material chemistry to design functional nanoparticles, self-assembled monolayers, or molecular complexes. In this paper, a mixture of only two basic precursors, such as the chloroauric acid (HAu(III)Cl4) and a thiol molecule (p-fluorothiophenol (p-HSPhF)), are used for the synthesis of gold(I)-thiolate coordination polymers. Under different conditions of synthesis and external stimuli, five different functional materials with different states of [Au(I)(p-SPhF)]n can be afforded. These gold-thiolate compounds are (i) red emissive, flexible, and crystalline fibers; (ii) composite materials made of these red emissive fibers and gold nanoparticles; (iii) amorphous phase; (iv) transparent glass; and (v) amorphous-to-crystalline phase-change material associated with an ON/OFF switch of luminescence. The different functionalities of these materials highlight the great versatility of the gold(I) thiolate coordination polymers with easy synthesis and diverse shaping that may have great potential as sustainable phosphors, smart textiles, sensors, and phase change memories.

Structural transformation of silver(i)–thiolate coordination polymer film at solid–liquid interfaces

Ligand exchange-induced structural transformation of silver–thiolate coordination polymers on a substrate.

Structure and Magnetic Properties of Pseudo-1D Chromium Thiolate Coordination Polymers

The synthesis, structure, and magnetic properties of two novel, pseudo-one-dimensional (1D) chromium thiolate coordination polymers (CPs), CrBTT and Cr2BDT3, are reported. The structures of these materials were determined using X-ray powder diffraction revealing highly symmetric 1D chains embedded within a CP framework. The magnetic coupling of this chain system was measured by SQUID magnetometry, revealing a switch from antiferromagnetic to ferromagnetic behavior dictated by the angular geometrical constraints within the CP scaffold consistent with the Goodenough-Kanamori-Anderson rules. Intrachain magnetic coupling constants JNN of -32.0 and +5.7 K were found for CrBTT and Cr2BDT3, respectively, using the 1D Bonner-Fisher model of magnetism. The band structure of these materials has also been examined by optical spectroscopy and density functional theory calculations revealing semiconducting behavior. Our findings here demonstrate how CP scaffolds can support idealized low-dimensional structural motifs and dictate magnetic interactions through tuning of geometry and inter-spin couplings.

Luminescent and sustainable d10 coinage metal thiolate coordination polymers for high-temperature optical sensing

The d10 coinage metal coordination polymers (CPs) are known to display photophysical properties which can be tuned depending on the functionality of the ligand. Three new CPs made of d10 coinage metals and methyl thiosalicylate, [M(o-SPhCO2Me)]n (M= Cu, Ag, Au), are reported. They are all constructed from one-dimensional metal-sulfur networks, in which Cu and Ag are three-coordinated to sulfur atoms, whereas Au is only two-coordinated. It results that both Cu(I) and Ag(I) CPs show orange photoemission at room temperature, and the Au(I) one exhibits near-infrared emission at low temperatures. The intense orange-emissive Ag(I) CP and the blue-emissive coumarin 120 have been mixed in an organic matrix, the polyvinylidene fluoride (PVDF), to form a dual luminescent flexible composite film. This film, evaluated for thermometry, shows great sensitivity for temperatures up to 100°C, a temperature never reached with non-lanthanide-based CPs.

Tuning the 1D-2D dimensionality upon ligand exchange in silver thiolate coordination polymers with photoemission switching.

Silver nanoparticles are known and widely used for their antimicrobial activities. Nevertheless, once they are released into the natural or biological environments, they can become toxic with time, because of the dissolution of some Ag(I) ions that can then react with thiol-based molecules, such as glutathione and/or compete with copper proteins. These assumptions are based on the high affinity of the soft acid Ag(I) and the soft base thiolates and the exchange reactions that are involved in complex physiological media. Here we synthesized and fully characterized two new 2D silver thiolate coordination polymers (CPs) that exhibit a reversible 2D-to-1D structural transformation in the presence of an excess of thiol molecules. This dimensionality change induces also a switch of the yellow emission of the Ag-thiolate CP. This study highlights that these highly stable silver-thiolate CPs, in basic, acidic and oxidant media can undergo a complete dissolution-recrystallization mechanism upon thiol exchange reactions.

Photoluminescence in halogeno copper(Ⅰ) methyl thiolate polymers via in situ DMSO decomposition reaction

Five halogeno-copper thiolate coordination polymers, Cu12Cl6(SCH3)6(DMSO) 1, Cu3X(SCH3)2 (2, 4), and Cu2X(SCH3) (X = Br, I) (3, 5) were solvothermally prepared by employing DMSO, which is used as a thiolate source via in situ decomposition. The X-ray crystallographic data revealed one type of 3D network structure composed of Atlas spheres. Additionally, two types of 2D layered bromo/iodo isostructural complexes were found, and the differences between these two types are attributed to the different connection modes of their Cu3X2(SCH3)2 chains. Sharing the halogen atoms in Cu3X2(SCH3)2 chain or bridging the chains via additional copper atoms could lead to the formation of different layers with a Cu:X:SCH3 ratio of 3:1:2 or 2:1:1, respectively. The absorption and emission spectral data described the influence of the ratio and species of halogen elements in copper thiolate complexes. From the spectroscopic studies, long-lived phosphorescence was detected, the characteristic lifetime of which depends on the crystal internal structures as well as the constituent halogen atoms.

A copper(I) thiolate coordination polymer with thermochromic and mechanochromic luminescence

A luminescent copper(I) thiolate coordination polymer named [Cu(pot)]n has been synthesized by the employment of the thiol ligand of 5-(3-pyridyl)-1,3,4-oxadiazole-2-thiol (Hpot). The maximum emission peak of [Cu(pot)]n at room temperature is located at 609 nm. The compound shows superb luminescent stability toward acidic/alkaline conditions and organic solvents. [Cu(pot)]n exhibits an interesting thermochromic behavior with the luminescence changing from saffron at 77 K to orange at 297 K and yellowish green at 497 K. Meanwhile, its luminescent color changes from orange to red after grinding. Thus, the compound represents a rare example of copper(I) thiolate coordination polymers possessing thermochromic and mechanochromic luminescence simultaneously.

Cyclic Solid-State Multiple Phase Changes with Tuned Photoemission in a Gold Thiolate Coordination Polymer.

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 AuI -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 AuI -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.

Cyclic Solid‐State Multiple Phase Changes with Tuned Photoemission in a Gold Thiolate Coordination Polymer

AbstractThe 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 AuI–thiolate coordination polymer which undergoes two successive phase changes on application of mild heating (&lt;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 AuI–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.

Frontispiz: Machine‐Learning‐Assisted Selective Synthesis of a Semiconductive Silver Thiolate Coordination Polymer with Segregated Paths for Holes and Electrons

Kristall-Engineering Die durch maschinelles Lernen unterstützte Synthese von halbleitenden Silberthiolat-Koordinationspolymeren mit segregierten Transportpfaden für Löcher und Elektronen wird von Daisuke Tanaka et al. im Forschungsartikel auf S. 23405 vorgestellt.

Frontispiece: Machine‐Learning‐Assisted Selective Synthesis of a Semiconductive Silver Thiolate Coordination Polymer with Segregated Paths for Holes and Electrons

Crystal Engineering The machine-learning-assisted selective synthesis of semiconductive silver thiolate coordination polymers with segregated paths for holes and electrons is reported by Daisuke Tanaka et al. in their Research Article on page 23217.

Machine-Learning-Assisted Selective Synthesis of a Semiconductive Silver Thiolate Coordination Polymer with Segregated Paths for Holes and Electrons.

Coordination polymers (CPs) with infinite metal-sulfur bond networks have unique electrical conductivities and optical properties. However, the development of new (-M-S-)n -structured CPs is hindered by difficulties with their crystallization. Herein, we describe the use of machine learning to optimize the synthesis of trithiocyanuric acid (H3 ttc)-based semiconductive CPs with infinite Ag-S bond networks, report three CP crystal structures, and reveal that isomer selectivity is mainly determined by proton concentration in the reaction medium. One of the CPs, [Ag2 Httc]n , features a 3D-extended infinite Ag-S bond network with 1D columns of stacked triazine rings, which, according to first-principle calculations, provide separate paths for holes and electrons. Time-resolved microwave conductivity experiments show that [Ag2 Httc]n is highly photoconductive (φΣμmax =1.6×10-4 cm2 V-1 s-1 ). Thus, our method promotes the discovery of novel CPs with selective topologies that are difficult to crystallize.

Machine‐Learning‐Assisted Selective Synthesis of a Semiconductive Silver Thiolate Coordination Polymer with Segregated Paths for Holes and Electrons

AbstractCoordination polymers (CPs) with infinite metal–sulfur bond networks have unique electrical conductivities and optical properties. However, the development of new (‐M‐S‐)n‐structured CPs is hindered by difficulties with their crystallization. Herein, we describe the use of machine learning to optimize the synthesis of trithiocyanuric acid (H3ttc)‐based semiconductive CPs with infinite Ag−S bond networks, report three CP crystal structures, and reveal that isomer selectivity is mainly determined by proton concentration in the reaction medium. One of the CPs, [Ag2Httc]n, features a 3D‐extended infinite Ag−S bond network with 1D columns of stacked triazine rings, which, according to first‐principle calculations, provide separate paths for holes and electrons. Time‐resolved microwave conductivity experiments show that [Ag2Httc]n is highly photoconductive (φΣμmax=1.6×10−4 cm2 V−1 s−1). Thus, our method promotes the discovery of novel CPs with selective topologies that are difficult to crystallize.

Lamellar silver thiolate coordination polymers with reversibly switchable blue-to-near infrared optical transitions

Lamellar silver thiolates (Ag-MPA) possess reversible temperature dependent blue-to-near infrared optical transitions resulting from metallophilic interactions in the layers and conformational stabilization of the ligands.

Self-assembling-directed Growth and PL Evolution of a Soluble Gold Thiolate Coordination Polymer

Herein we report the synthesis of Au(I) thiolate coordination polymers with PEGylated side chains in water, highlighting significant effects of the alkyl spacer to promote the size growth and PL ev...

Post-synthetic functionalization and ligand exchange reactions in gold(i) phenylthiolate-based coordination polymers

Post-modification and ligand exchange reactions from 1D or 2D gold thiolate coordination polymers occur through a dissolution–recrystallization pathway.

Transparent and luminescent glasses of gold thiolate coordination polymers.

Obtaining transparent glasses made of functional coordination polymers (CPs) represents a tremendous opportunity for optical applications. In this context, the first transparent and red-emissive glasses of gold thiolate CPs have been obtained by simply applying mechanical pressure to amorphous powders of CPs. The three gold-based CP glasses are composed of either thiophenolate [Au(SPh)] n , phenylmethanethiolate [Au(SMePh)] n or phenylethanethiolate [Au(SEtPh)] n . The presence of a longer alkyl chain between the thiolate and the phenyl ring led to the formation of glass with higher transparency. The glass transitions, measured by thermomechanical analysis (TMA), occurred at lower temperature for CPs with longer alkyl chains. In addition, all three gold thiolate glasses exhibit red emission at 93 K and one of them, [Au(SMePh)] n , remains luminescent even at room temperature. An in-depth structural study of the amorphous gold thiolates by XRD, PDF and EXAFS analysis showed that they are formed of disordered doubly interpenetrated helical chains. These d10 metal-based compounds represent the first examples of transparent and luminescent CP glasses.

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

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.

Reactions Coupled Self- and Co-Assembly: A Highly Dynamic Process and the Resultant Spatially Inhomogeneous Structure.

Reactions coupled self-assembly represents a step forward towards biomimetic behavior in the field of supramolecular research. Here, two pH-dependent reactions of thiol-disulfide exchange and ligand exchange were used to couple with the self-assembly of an AuI -thiolate coordination polymer consisting of two ligands. Thanks to the comparable rates between the reactions and self-assembly, the compositions of the assemblies change continuously with time, resulting in a highly dynamic assembly process and spatially inhomogeneous structure that are very common in life systems but cannot be easily obtained with one-pot artificial methods.

New Lamellar Silver Thiolate Coordination Polymers with Tunable Photoluminescence Energies by Metal Substitution

The structures of two lamellar silver thiolate coordination polymers [Ag( p-SPhCO2H)] n (1) and [Ag( p-SPhCO2Me)] n (2) are described for the first time. Their inorganic part is composed of distorted Ag3S3 honeycomb networks separated by noninterpenetrated thiolate ligands. The main difference between the two compounds arises from dimeric hydrogen bonds present for the carboxylic acids. Indepth photophysical studies show that the silver thiolates exhibit multiemission properties, implying luminescence thermochromism. More interestingly, the synthesis of a heterometallic lamellar compound, [Ag0.85Cu0.15( p-SPhCO2H)] n (3), allows to obtain mixed metal thiolate coordination polymers and to tune the photophysical properties with the excitation wavelengths from a green vibronic luminescence to a single red emission band.