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Two-dimensional transition metal dichalcogenides and semiconductor metal oxides have shown great potential in photocatalysis. However, their stability and efficiency need to be further improved. In this paper, porous ZnO nanorods with high specific surface area were prepared from metal-organic framework ZIF-8 by a simple hydrothermal method. A MoS2/ZnO composite was constructed by loading MoS2 onto the surface of porous ZnO nanorods. Compared with ZnO materials prepared by other methods, MoS2/ZnO prepared in this paper exhibits superior photocatalytic performance. The enhanced photocatalytic activity of the MoS2/ZnO composite can be attributed to the formation of heterojunctions and strong interaction between them, which greatly facilitate the separation of electrons and holes at the contact interface. In addition, due to the wide absorption region of the visible spectrum, MoS2 can greatly broaden the light absorption range of the material after the formation of the composite material, increase the utilization rate of visible light, and reduce the combination of electrons and holes. This study provides a new way to prepare cheap and efficient photocatalysts. [ABSTRACT FROM AUTHOR]

Marine heterotrophic prokaryotes primarily take up ambient substrates using transporters. The patterns of transporters targeting particular substrates shape the ecological role of heterotrophic prokaryotes in marine organic matter cycles. Here, we report a size-fractionated pattern in the expression of prokaryotic transporters throughout the oceanic water column due to taxonomic variations, revealed by a multi-"omics" approach targeting ATP-binding cassette (ABC) transporters and TonB-dependent transporters (TBDTs). Substrate specificity analyses showed that marine SAR11, Rhodobacterales, and Oceanospirillales use ABC transporters to take up organic nitrogenous compounds in the free-living fraction, while Alteromonadales, Bacteroidetes, and Sphingomonadales use TBDTs for carbon-rich organic matter and metal chelates on particles. The expression of transporter proteins also supports distinct lifestyles of deep-sea prokaryotes. Our results suggest that transporter divergency in organic matter assimilation reflects a pronounced niche separation in the prokaryote-mediated organic matter cycles. [ABSTRACT FROM AUTHOR]

Organic metal complexes (OMCs) transport trace metals (e.g. , Co, Ni, Cu) from surface soils, via the unsaturated zone, to sites of cave carbonate (speleothem) formation. OMCs clearly imprint on speleothem trace element chemistry, but the role of kinetic factors in the signal transfer process has yet to be elucidated. We investigated whether OMCs may viably link metal concentrations in stalagmites and local hydrology (i.e. , drip rate), via their time-sensitive dissociation (or 'decay') in the speleothem water thin-film. We performed competitive ligand exchange experiments using water and soil samples from eight geographically diverse Aotearoa New Zealand caves, providing a first comparative characterisation of speleothem-specific OMC kinetics. Critically, this approach corroborated that NOM ligands limit transition metal availability at the dripwater-speleothem interface, exhibiting stabilities on the order Cu ≈ Co > Ni, whereas organic complexation of the alkaline earth metals Mg and Sr was virtually absent. Systematic variations of OMC stability with natural organic matter characteristics were not observed amongst water samples, whilst enhanced complexation was clearly evident in the comparably organic-rich soil extracts. Our results imply that the supply of transition metals to speleothems is inversely related to drip rate, increasing with drip interval via the decay of OMCs. This process appears most sensitive on time-scales relevant to typical speleothem-forming settings (<0 to ca. 40 drips min−1, corresponding to ca. <5.6 mL min−1), and therefore provides a general, mechanistic link to a quantitative proxy of palaeoclimatic cave drip rates. [ABSTRACT FROM AUTHOR]

Despite the enormous efforts to control the growth behavior of Li, achieving a dendrite‐free Li deposition and high‐energy‐density have remained an inevitable challenge of Li metal batteries. Here, the conformal deposition of Li metal is reported on electroactive organic materials to achieve a high‐energy‐density and electrochemical longevity. To this end, Li2C8H4O4 (Li2TP), which can act as both the electrode material (providing the redox capacity) and Li host (inducing the dendrite‐free Li deposition), is used as the model electroactive organic material. The Li2TP host exhibits reversible sequential lithiation/delithiation and Li deposition/stripping reactions. Consequently, a Li‐free full cell constructed by the Li2TP host (without pre‐charging) and a LiFePO4 cathode delivered a high areal capacity (≈3.8 mAh cm−2), exceptional rate performance (≤12 mA cm−2), and superior cyclability (80% capacity retention after 100 cycles). This electroactive organic material‐based Li host strategy can provide a new perspective for the development of practical Li metal batteries. [ABSTRACT FROM AUTHOR]

Owing to well‐defined structure as well as easy synthesis and modification, metal‐organic frameworks (MOFs) have emerged as promising catalysts for tandem reactions. In this article, we aim to summarize the development of multifunctional MOFs, including mixed metal MOFs, MOFs that are synergistically catalyzed by metal nodes and organic linkers, MOFs loaded with metal nanoparticles, etc, as heterogenous catalysts for tandem reactions over the past five years. This concept briefly discusses on present challenges, future trends, and prospects of multifunctional MOFs catalysts in tandem reactions. [ABSTRACT FROM AUTHOR]

With the rapid development of anion exchange membrane technology and the availability of high-performance non-noble metal cathode catalysts in alkaline media, the commercialization of anion exchange membrane fuel cells has become feasible. Currently, anode materials for alkaline anion-exchange membrane fuel cells still rely on platinum-based catalysts, posing a challenge to the development of efficient low-Pt or Pt-free catalysts. Low-cost ruthenium-based anodes are being considered as alternatives to platinum. However, they still suffer from stability issues and strong oxophilicity. Here, we employ a metal–organic framework compound as a template to construct three-dimensional porous ruthenium–tungsten–zinc nanocages via solvothermal and high-temperature pyrolysis methods. The experimental results demonstrate that this porous ruthenium–tungsten–zinc nanocage with an electrochemical surface area of 116 m2 g−1 exhibits excellent catalytic activity for hydrogen oxidation reaction in alkali, with a kinetic density 1.82 times and a mass activity 8.18 times higher than that of commercial Pt/C, and a good catalytic stability, showing no obvious degradation of the current density after continuous operation for 10,000 s. These findings suggest that the developed catalyst holds promise for use in alkaline anion-exchange membrane fuel cells. [ABSTRACT FROM AUTHOR]

Photocatalytic reactions involving a reductive radical‐polar crossover (RRPCO) generate intermediates with carbanionic reactivity. Many of these proposed intermediates resemble highly reactive organometallic compounds. However, conditions of their formation are generally not tolerated by their isolated organometallic versions and often a different reactivity is observed. Our investigations on their nature and reactivity under commonly used photocatalytic conditions demonstrate that these intermediates are indeed best described as free, superbasic carbanions capable of deprotonating common polar solvents usually assumed to be inert such as acetonitrile, dimethylformamide, and dimethylsulfoxide. Their basicity not only towards solvents but also towards electrophiles, such as aldehydes, ketones, and esters, is comparable to the reactivity of isolated carbanions in the gas‐phase. Previously unsuccessful transformations thought to result from a lack of reactivity are explained by their high reactivity towards the solvent and weakly acidic protons of reaction partners. An intuitive explanation for the mode of action of photocatalytically generated carbanions is provided, which enables methods to verify reaction mechanisms proposed to involve an RRPCO step and to identify the reasons for the limitations of current methods. [ABSTRACT FROM AUTHOR]

A series of 5-alkoxy-1,3-benzenedicarbaldehydes and related dimers were prepared in three steps from dimethyl 5-hydroxyisophthalate. Acid catalyzed condensation of the dialdehydes with a tripyrrane dicarboxylic acid, followed by oxidation with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, afforded good yields of 3-alkoxybenziporphyrins, although dimeric tetraaldehydes failed to give isolatable porphyrinoid products. Proton NMR spectroscopy gave no indication of an aromatic ring current, but addition of trifluoroacetic acid resulted in the formation of dications that exhibited weakly diatropic characteristics. Spectroscopic titration with TFA demonstrated that stepwise protonation took place, generating monocationic and dicationic species. 3-Alkoxybenziporphyrins reacted with nickel(II) or palladium(II) acetate to give the related nickel(II) or palladium(II) complexes. These stable organometallic derivatives showed increased diatropic properties that were most pronounced for the palladium(II) complexes. These unique porphyrinoids provide further insights into the properties of benziporphyrins. [ABSTRACT FROM AUTHOR]

A lactate-depleting MOF-based cascade catalytic nanoplatform, which could deplete lactate alleviates to facilitate the tumor vascular normalization for T cell infiltration yet produce H 2 O 2 for autocatalytic Fenton reaction to induce Immunogenic cell death for T cell activation, is engineered to reinforce T cell response based on a "two birds with one stone" strategy. [Display omitted] • A lactate-depleting MOF-based catalytic nanoplatform LZM, is engineered to reinforce T cell response based on a "two birds with one stone" strategy-to promote vascular normalization and facilitate T cell infiltration. • LZM could simultaneously induce the ICD, normalize tumor microvessels and activate the T cells through cascade catalytic reactions producing a large amount of hydroxyl radicals. • LZM could efficiently inhibit tumor growth and strengthen anti-PD1 efficacy. • Transcriptomic analysis revealed that LZM-regulated genes were significantly enriched in PPAR-related signaling pathways and metabolism-related signaling pathways. Infiltration and activation of intratumoral T lymphocytes are critical for immune checkpoint blockade (ICB) therapy. Unfortunately, the low tumor immunogenicity and immunosuppressive tumor microenvironment (TME) induced by tumor metabolic reprogramming cooperatively hinder the ICB efficacy. Herein, we engineered a lactate-depleting MOF-based catalytic nanoplatform (LOX@ZIF-8@MPN), encapsulating lactate oxidase (LOX) within zeolitic imidazolate framework-8 (ZIF-8) coupled with a coating of metal polyphenol network (MPN) to reinforce T cell response based on a "two birds with one stone" strategy. LOX could catalyze the degradation of the immunosuppressive lactate to promote vascular normalization, facilitating T cell infiltration. On the other hand, hydrogen peroxide (H 2 O 2) produced during lactate depletion can be transformed into anti-tumor hydroxyl radical (•OH) by the autocatalytic MPN-based Fenton nanosystem to trigger immunogenic cell death (ICD), which largely improved the tumor immunogenicity. The combination of ICD and vascular normalization presents a better synergistic immunopotentiation with anti-PD1, inducing robust anti-tumor immunity in primary tumors and recurrent malignancies. Collectively, our results demonstrate that the concurrent depletion of lactate to reverse the immunosuppressive TME and utilization of the by-product from lactate degradation via cascade catalysis promotes T cell response and thus improves the effectiveness of ICB therapy. [ABSTRACT FROM AUTHOR]

The present investigation aims to improve the efficiency of fungal mono- and mixed cultures in removing organic pollutants and metals from sewage water (SW) for further maize plant response assessments. The reduction in the organic load from the SW was harnessed using a co-culture consortium consisting of Aspergillus niger (KB5), Sordariomycetes sp. (D10), and Coniochaetaceae sp. (LB3). The testing results had evinced removal of up to 88% of the organic matter and more than 96%, 91%, 80%, and 47.6%, of removal percentages for Copper (Cu), Nickel (Ni), Cadmium (Cd), and Lead (Pb), respectively, with the developed fungal consortium [KB5 + D10 + LB3]. After treatment and lab experiments, a reuse of treated and untreated SW for plant irrigation was evaluated towards improving maize plant growth. Irrigation was conducted in pot experiments with three types of water: clean water (Control), untreated (USW), and treated SW by fungal consortia (TSW) and by station treatment plant STP (TSWP) using the randomized complete block (RCB) experimental design. Results of the pots trial revealed that the morphological parameters of SW-irrigated plants are slightly improved compared to water-irrigated plants. Data regarding assimilating area attributes indicated that the most significant enlargement of the assimilation area was observed with TSW-D (1/4) irrigation by 1051 cm2, followed by TSWP-D (0) by 953.96 cm2, then USW-D (1/4) by 716.54 cm2, as compared to plants irrigated with clean water (506.91 cm2). On average, the assimilation areas were larger by 51.76%, 46.86%, and 29.25% in TSW, USW, and TSWP-irrigated plants, respectively. Thus, SW irrigation supports the required qualities and quantities of microelements and water for plant growth. Oxidative stress assessment showed that irrigations with treated SW caused a significant decrease in both enzymatic and non-enzymatic antioxidants, depicting that the treatment lowered the stress of sewage water. [ABSTRACT FROM AUTHOR]

While cytochrome P450 (CYP; P450) enzymes are commonly associated with the metabolism of organic xenobiotics and drugs or the biosynthesis of organic signaling molecules, they are also impacted by a variety of inorganic species. Metallic nanoparticles, clusters, ions, and complexes can alter CYP expression, modify enzyme interactions with reductase partners, and serve as direct inhibitors. This commonly overlooked topic is reviewed here, with an emphasis on understanding the structural and physiochemical basis for these interactions. Intriguingly, while both organometallic and coordination compounds can act as potent CYP inhibitors, there is little evidence for the metabolism of inorganic compounds by CYPs, suggesting a potential alternative approach to evading issues associated with rapid modification and elimination of medically useful compounds. [ABSTRACT FROM AUTHOR]

Two new metal–organic multi-component compounds of Ni(II) and Co(II), viz. [Ni(3-CNpy)2(H2O)4]ADS·2.75H2O (1) and [Co(3-CNpy)2(H2O)4](4-ClbzSO3)2 (2) (3-CNpy = 3-cyanopyridine, ADS = anthraquinone-1,5-disulfonate, 4-ClbzSO3 = 4-chlorobenzenesulfonate), were synthesized and characterized using single crystal XRD, TGA, spectroscopic (IR, electronic) and elemental analyses. Both the compounds crystallize as multi-component compounds of Ni(II) and Co(II), with uncoordinated ADS and 4-ClbzSO3 moieties in the crystal lattice, respectively. Crystal structure analyses revealed the presence of antiparallel nitrile···nitrile and π-stacked assemblies involving alternate coordinated 3-CNpy and uncoordinated ADS and 4-ClbzSO3 moieties. Moreover, unconventional charge reverse Cl∙∙∙N halogen bonding contacts observed in compound 2 provide additional reinforcement to the crystal structure. Theoretical calculations confirm that the H-bonding interactions, along with anion–π(arene) and anion–π(CN) in 1 and π–π, antiparallel CN···CN and charge reverse Cl···N halogen bonds in 2, play crucial roles in the solid state stability of the compounds. In vitro anticancer activities observed through the trypan blue cell cytotoxicity assay reveal that the compounds induce significant concentration dependent cytotoxicity in Dalton's lymphoma (DL) cancer cells, with nominal effects in normal healthy cells. Molecular docking studies reveal that the compounds can effectively bind with the active sites of anti-apoptotic proteins, which are actively involved in cancer progression. [ABSTRACT FROM AUTHOR]

Ferrocene has a unique structure, i.e., a central iron atom neatly sandwiched between two cyclopentadienyl rings, which has revolutionized the chemists' views about how metals bind to organic π-systems. This structural arrangement leads to some fascinating chemical and photophysical properties. The last three decades, there were reports about receptor molecules that could be considered to perform simple logic operations via coupling ionic bonding or more complex molecular-recognition processes with photonic (fluorescence) signals. In these systems, chemical binding ('input') results in a change in fluorescence intensity ('output') from the receptor. It has been proven that molecules respond to changes in their environment, such as the presence of various ions, neutral species, pHs, temperatures, and viscosities. Since their first realization by de Silva, molecular logic gates have been intensively experimentally studied, with purely theoretical studies being less common. Here, we present the research that has been conducted on Molecular Logic Gates (MLGs) containing ferrocene and their applications. We categorized such systems into three families of MLGs: long-chain molecules (oligomers or polymers) that incorporate ferrocene, medium-sized molecules that incorporate ferrocene, and systems where ferrocene or its derivatives are used as external additives. Furthermore, MLGs including metal cations without the ferrocene moiety are briefly presented, while computational methodologies for an accurate theoretical study of MLG, including metal cations, are suggested. Finally, future perspectives of MLGs containing ferrocene and their applications are also presented. [ABSTRACT FROM AUTHOR]

Shape alterations of molecular systems, induced by their (electric) charging/discharging, could facilitate useful electronic and/or mechanical functions in molecular-scale devices and machines. The present study reports structures, stabilities, charge distributions, and IR spectra for a group of complexes of a main-group metalloid (boron) atom with hydrocarbon molecules. The considered systems include the smallest species demonstrating the basic principle of operation, as well as their size-extended analogues, generalizing it to larger counterparts based on such units. The system geometries vary considerably between neutral and ionic counterparts and exhibit two–three typical conformations related to twisting by up to about 90 degrees. The predicted structures correlate with specific infrared spectra, which can enable their experimental identification and transformation tracking. The above-mentioned characteristics suggest the potential utility of such systems for intermolecular switches, with the possible spectral monitoring of their functioning. [ABSTRACT FROM AUTHOR]

Ladder systems situated in the dimensional crossover region have attracted much attention because their electronic states and physical properties depend strongly on the electronic correlations among the constituent legs. Generally, two‐/three‐legged transition metal‐oxide ladder compounds are studied as representative ladder systems, but two‐/three‐dimensional (2D/3D) extensions based on such ladder systems with a few numbers of legs are difficult because of the extreme synthesis conditions. Here, for the first time, we report the successful creation of a 3D extended two‐legged ladder compound, [Pt(en)(dpye)I]2(NO3)4 ⋅ 2H2O (en=ethylenediamine; dpye=1,2‐Di(4‐pyridyl)ethane), which is obtained by simple oxidative polymerization of a small Pt macrocyclic complex using elemental I2. The unique 3D extended lattice consists of 1D mixed‐valence halogen‐bridged metal chains (⋅⋅⋅Pt−I−Pt−I⋅⋅⋅) and helically arranged macrocyclic units as the constituent legs and rungs, as confirmed by single‐crystal X‐ray diffraction. Diffuse X‐ray scattering analyses and optical measurements revealed that the out‐of‐phase mixed‐valence Pt2+/Pt4+ arrangement arises from the weak interchain correlation among adjacent legs. In addition, this compound shows an increase in proton conductivity by a factor of up to 1000, depending on humidity. [ABSTRACT FROM AUTHOR]

A feasible yet effective electrochemical aptasensor for the detection of 25-hydroxyvitamin D3 (25-OHD3) has been devised based on gold-modified mesoporous silica-zeolitic imidazolate framework-8 (MSS-Z8) composite. The physical as well as electrochemical aspects of Au/MSS/FTO, Au/Z8/FTO, and Au/MSS-Z8/FTO were thoroughly investigated, and Au/MSS-Z8/FTO displayed enhanced electrochemical and electrokinetic performance. Therefore, Au/MSS-Z8/FTO platform has been utilized for electrochemical biosensing of 25-OHD3 by employing 5' thiolated aptamer specific to 25-OHD3 as biorecognition element. The efficacy of resultant aptasensor was evaluated in [Fe(CN)6]3−/4− redox mediator using differential pulse voltammetry technique. The Apt/Au/MSS-Z8/FTO displayed a highly sensitive (39.1 µA (pg mL−1)−1 cm−2) and selective voltammetric response towards 25-OHD3 within 0.001 to 106 pg mL−1 concentration range with experimental and theoretical detection limit of 0.001 and 0.084 pg mL−1, respectively. Also, the aptasensor performed reliably with both spiked serum samples (Recovery = 97.56–102.1%, RSD = 0.89–2.80%) as well as real serum samples as evident by consistency of results with those obtained from ELISA analysis of real serum samples. [ABSTRACT FROM AUTHOR]

As a hybrid material, metal organic frameworks (MOFs) contain unique characteristics for biomedical applications such as high porosity, large surface area, different crystalline morphologies, and nanoscale dimensions. These frameworks are assembled through the interconnection of organic linkers with metal nodes, while the engineering of an MOF for biomedical applications requires versatile linkers with acceptable symmetry. Porphyrin, as an organic linker with interesting photochemical and photophysical properties, attracted the attention of many for engineering the potent multifunctional porphyrinic metal organic frameworks (PMOFs). In this regard, a large number of approaches were conducted for designing robust practical PMOFs with a wide range of applications. In this review, we introduced another perspective of MOFs and coordination polymers constructed from porphyrinic linkers with a special focus on those synthesized by meso-tetrakis (4-carboxyphenyl) porphyrin (TCPP). In the following, we summarized and discussed the different types of PMOFs and their biomedical applications in terms of diagnostic agent, therapeutic platform, and drug delivery vehicle. [ABSTRACT FROM AUTHOR]

• The recent progress of different reactions in electrocatalysis is reviewed. • The development of metal-organic skeleton compounds (MOFs) in electrocatalysis was reviewed. • The research focus and prospect of electrocatalysis are prospected. Metal-organic frameworks (MOFs) have favorable characteristics such as large specific surface area, high porosity, structural diversity, and pore surface modification, giving them great potential for development and attractive prospects in the research area of modern materials electrocatalysis. However, unsatisfactory catalytic activity and poor electronic conductivity are the main challenges facing MOFs. This review focuses on MOF-based materials used in electrocatalysis, based on the types of catalytic reactions that have used MOF-based materials in recent years along with their applications, and also looks at some new electrocatalytic materials and their future development prospects. [Display omitted] [ABSTRACT FROM AUTHOR]

Nucleation of particles into crystalline structures can be observed in a wide range of systems from metallic and metal–organic compounds to colloidal and polymeric patch particles. Here, we perform kinetic Monte Carlo simulations to study the nucleation kinetics of particles with different ligancies z at constant supersaturation s. This approach allows one to determine several physico-chemical quantities as a function of s, including the growth probability P(n), the critical nucleus size n*, and the stationary nucleation rate Js. Our numerical results are rationalized in terms of a self-consistent nucleation theory where both n* and Js present a non-trivial dependence on s, but which can be determined from the values of effective z-dependent parameters. [ABSTRACT FROM AUTHOR]

The interaction between nonmetal and metal atoms has attracted great interest in the development of organometallic compounds and their promising applications. In this study, we explored the interaction between boron and thorium atoms, based on the stable B40Th coordination compound, by employing density functional theory calculations. We elucidated the stability and geometries of the B40Th coordination compound and revealed the electron transfer from the metal atom Th to B40, which is evidenced by the natural bond orbital calculations. This electron transfer is attributed to the electron-withdrawing character of the boron atom and results in clear electrostatic interaction. Additionally, bond critical analysis and bond order calculations show obvious covalent characters between the metal and nonmetal atoms. The IR spectrum was simulated to give detailed information to identify this targeted compound in future experiments. This study is expected to enhance the understanding of metal–nonmetal interactions and provides useful information for constructing new organometallic compounds based on actinium metal atoms. [ABSTRACT FROM AUTHOR]

Palladium films hold signicance due to their remarkable affinity for hydrogen diffusion, rendering them valauble for the seperation and purification of hydrogen in membrane reactors. However, palladium is expensive, and its films can become brittle after only a few cycles of hydrogen separation. Alloying with silver has been shown to overcome the problem of palladium embrittlement. Palladium‐silver films have been produced via several methods but all have drawbacks, such as difficulties controlling the alloy composition. This study explores two promising jet printing methods: Inkjet and Aerosoljet. Both methods offer potential advantages such as direct patterning, which reduces waste, enables thin film production, and allows for the control of alloy composition. For the first time, palladium‐silver alloys have been produced via inkjet printing using a palladium‐silver metal organic decomposition (MOD) ink, which alloys at a temperature of 300 °C with nitrogen. Similarly, this study also demonstrates a pioneering approach for Aerosol Jet printing, showing the potential of a novel room‐temperature method, for the deposition of palladium‐silver MOD inks. This low temperature approach is considered an important development as palladium‐silver MOD inks are originally designed for deposition on heated substrates. [ABSTRACT FROM AUTHOR]

This article discusses the synthesis of allyl and alkynyl glycosides using a tris(pentafluorophenyl)borane catalyst. The authors explore different reagent systems and catalysts used for this synthesis, highlighting their advantages and limitations. They also present their own findings on the synthesis of 2,3-unsaturated C-allyl and alkynyl glycosides using tris(pentafluorophenyl)borane as a catalyst. The article provides information on the reaction conditions, optimization, and efficiency of the synthesis. The text also describes the synthesis and characterization of various compounds, providing useful information for researchers studying these compounds or related topics. The authors acknowledge the support they received from the National Fellowship for Other Backward Classes and CSIR, as well as the SAIF Division of CSIR-CDRI for providing spectroscopic and analytical data. [Extracted from the article]

A series of bidentate, viz., 1,1'-(1,2-ethylene)-3,3'-dimethyldiimidazoline-2,2'-diylidene (L1), 1-methyl-3-(2-pyridylmethyl)-imidazoline-2-ylidene (L2) and tridentate, viz., 1,3-bis(2-pyridyl)-imidazoline-2-ylidene (L3) ligands have been obtained from their corresponding imidazolium salts through deprotonation reactions. Treatment of UO2Cl2(THF)3 with one equivalent L3 produces air-stable U(VI)-carbene complex 3, characterized by elemental analysis, FTIR, NMR spectroscopy as well as extended X-ray absorption fine structure (EXAFS) analysis. EXAFS result indicates that the ligand is bonded through one C and two N-atoms to the uranium atom. Attempts to synthesize uranyl complexes derived from L1 and L2 were also successful but these complexes are decomposed quickly within one hour at room temperature. 3 produces pure UO2 powder when heated under an argon atmosphere from room temperature to 600 °C with constant heating rate of 5 °C/min. The solid-state UV–Vis spectrum of the compound shows absorption peaks at 332 and 450 nm. The excitation spectrum of 3 (at λem = 520 nm) exhibits two almost symmetrical peaks at 273 and 368 nm. Density functional theory-based quantum mechanical calculations indicate that a partial covalent interaction exists between the carbene C and U while a weak non-covalent interaction exists between carbene N and U atoms. [ABSTRACT FROM AUTHOR]

As we delve deeper into the world of chemistry, we find ourselves continually amazed by the innovative and cutting-edge techniques being developed. One such technique that has garnered significant attention is spectroelectrochemistry, a field that promises to revolutionise the way we study the redox behaviour of organometallic and coordination compounds. At its core, spectroelectrochemistry is a technique that combines electrochemistry and spectroscopy to offer insight into the electron transfer properties and mechanism through the characterisation of electron transfer processes and redox events. This innovative technique is rapidly gaining popularity among the researchers and is being widely adopted as a go-to method for studying the electrochemical properties of the molecules. One of the key advantages of spectroelectrochemistry is a powerful information about the redox behaviour of organometallic and coordination compounds. By combining synthesis-oriented electrochemistry with analysis-focused spectroscopy techniques, researchers are able to gain unprecedented insights into the electronic structure and reactivity of these complex systems. This tutorial review is focused on the current state-of-the-art of spectroelectrochemistry applied for the study of the redox behaviour of organometallic and coordination compounds. The development and teaching of the methodology of spectroelectrochemistry are demonstrated using specific examples. [ABSTRACT FROM AUTHOR]

This paper utilizes the TFA-MOD (Trifluoroacetate Metal-Organic Decomposition) method to prepare YB 2 C 3 O 7-δ (YBCO) superconducting films on a LaMnO 3 metal substrate. Using a self-made process curve, we investigate the nucleation and growth orientation of crystals at various temperatures under specific oxygen partial pressures (P O2). We successfully obtain an oxygen partial pressure-temperature phase diagram at a fixed time. This diagram provides critical insight into the trends that guide our regulation of parameters to ultimately achieve a relatively pure a -axis oriented YBCO film. Temperature and nucleation rate are important parameters that influence crystal nucleation orientation. The key conditions for producing a -axis-oriented YBCO films include low temperature, high Δ μ , and extended crystallization time. [ABSTRACT FROM AUTHOR]

This research article presents a comprehensive study on the prediction of thermal conductivity (TC) as a primary outcome for an artificial neural network (ANN) model in the context of nanoenhanced phase change materials (NEPCMs). To improve predictive accuracy and to reduce variation within the NEPCM dataset, a targeted dataset was employed, consisting exclusively of NEPCMs synthesized using paraffin wax (PW) and metal oxide nanoparticles. Unlike existing empirical models that predict TC of NEPCM without simultaneously considering multiple factors influencing it, this study integrates multiple factors, providing a more accurate prediction of NEPCM thermal conductivity. Additionally, the study explores the impact of synthesis parameters on the thermal performance of NEPCMs, focusing on the examination of factors such as the melting temperature of pure phase change material (PCM), nanoparticle size, and NEPCM composition. The thermal characterizations demonstrate outstanding thermophysical properties in NEPCMs, particularly in terms of thermal conductivity, phase change enthalpy, and thermal stability compared to their respective base PCM. An ANN TC prediction model demonstrates exceptional correlation (>99%) with reported NEPCMs, providing a reliable tool for TC forecasting in similar NEPCM categories. The backpropagation ANN model predicts NEPCM TC with a mean squared error (MSE) of 0.031124 within eight epochs. The dataset used exhibits high fit values, with R -values of 0.99825, 0.99208, and 0.9824 for training, validation, and testing, respectively. These values closely match experimentally determined TC, with less than 4% error. [ABSTRACT FROM AUTHOR]

β‐Glucosidase, a pivotal enzyme in the synthesis of various glycosides with wide applications in industries such as food, cosmetics, beverages, bioenergy, nutraceuticals, pharmaceuticals, and detergents, undergoes immobilization to enhance its utility in industrial processes and improve enzymatic properties. In this study, the conventional hybrid nanoflower synthesis method was used for β‐glucosidase‐inorganic hybrid nanoflowers. Following a comprehensive pH and temperature scanning of the nanoflowers, the influence of metallic ions and various organic solvents on hybrid nanoflowers to enhance the activity and stability of the biocatalyst were investigated. The optimal morphology for β‐Glu/NFs was determined to be 0.01 mg/mL. To obtain the optimum activity conditions, we explored pH values ranging from 3 to 8 and temperatures between 30 and 80 °C. Both the free form and β‐Glu/NFs exhibited higher activity in acidic conditions, with a significant decrease in activity observed at pH 7 and 8. β‐Glu/NFs demonstrated superior activity compared to the free enzyme in the presence of metal ions, exhibiting a remarkable 3.6‐fold increase in activity in chloroform, and approximately 2.8 and 2.7 times increase in benzene and glycerol, respectively. Moreover, it displayed over a 2‐fold increase in activity in methanol, ethanol, isopropanol, n‐butanol, acetone, and DMSO. [ABSTRACT FROM AUTHOR]

Smart materials based on stimuli-fluorochromic π-conjugated solids (SFCSs) have aroused significant interest due to their versatile and exciting properties, leading to advanced applications. In this review, we highlight the recent developments in SFCS-based smart materials, expanding beyond organometallic compounds and light-responsive organic luminescent materials, with a discussion on the design strategies, exciting properties and stimuli-fluorochromic mechanisms along with their potential applications in the exciting fields of encryption, sensors, data storage, display, green printing, etc. The review comprehensively covers single-component and multi-component SFCSs as well as their stimuli-fluorochromic behaviors under external stimuli. We also provide insights into current achievements, limitations, and major challenges as well as future opportunities, aiming to inspire further investigation in this field in the near future. We expect this review to inspire more innovative research on SFCSs and their advanced applications so as to promote further development of smart materials and devices. [ABSTRACT FROM AUTHOR]

The current work reports on the synthesis, crystal structure and optoelectronic properties of (Me3S)2ZrCl6, prepared by reacting the solid precursors (Me3S)Cl and ZrCl4 in pyrex tubes at 150 °C under vacuum. According to X-ray powder diffraction and Rietveld analysis, (Me3S)2ZrCl6 crystallizes in the cubic space group Pa-3 (No. 205) with a = 12.4664(1) Å. The crystal structure consists of isolated trigonal pyramidal trimethylsulfonium cations and octahedral [ZrCl6]2- anions with weak hydrogen bonds among them and no signs of structural disorder. This 0D-material is stable in air and dissolves in water and dimethylformamide. Raman spectroscopy shows characteristic vibrational modes for the organic and inorganic moieties over the frequency range of 5–3200 cm−1. UV-Vis spectroscopy reveals a large band gap of 5.1 eV and a broadband luminescence with emission maximum at 465 nm in the solid state. The luminescent properties of (Me3S)2ZrCl6 are discussed and compared with those of similar inorganic or metal-organic compounds. [ABSTRACT FROM AUTHOR]

This article provides an overview of the synthesis and applications of planar chiral ferrocene derivatives. It discusses two main approaches to introducing planar chirality in ferrocene compounds: base-mediated ortho-metallation and transition-metal-catalyzed C-H bond activations. These methods allow for the introduction of various functional groups and have applications in asymmetric catalysis, medicinal chemistry, and materials science. The authors, Tomáš Čarný and Radovan Šebesta, are experts in organic chemistry and have conducted research in the field of ferrocene derivatives. [Extracted from the article]

Indole is an important element of many natural and synthetic molecules with significant biological activity. Nonetheless, the co-presence of transitional metals in organic scaffold may represent an important factor in the development of effective medicinal agents. This review covers some of the latest and most relevant achievements in the biological and pharmacological activity of important indole-containing metal complexes in the area of drug discovery. [ABSTRACT FROM AUTHOR]

This review presents a comprehensive evaluation for the manufacture of organic molecules via efficient microfluidic synthesis. Microfluidic systems provide considerably higher control over the growth, nucleation, and reaction conditions compared with traditional large-scale synthetic methods. Microfluidic synthesis has become a crucial technique for the quick, affordable, and efficient manufacture of organic and organometallic compounds with complicated characteristics and functions. Therefore, a unique, straightforward flow synthetic methodology can be developed to conduct organic syntheses and improve their efficiency. [ABSTRACT FROM AUTHOR]

Additive manufacturing techniques such as vat photopolymerization have laid the foundation for impressive advances in the 3D structuring of ceramic materials. However, simultaneous structuring of these complex‐shaped ceramic objects on the sub‐µm scale, an essential feature for a wide range of applications in separation, energy conversion and storage, adsorption or sensing, has remained a tremendous challenge. This study demonstrates how complex‐shaped polymer‐derived SiOC ceramics exhibiting hierarchical porosity ranging from the sub‐µm‐ to the millimeter‐range can be generated by combining vat photopolymerization with photopolymerization‐induced phase separation using preceramic polymer‐based phase‐separating resins. In addition to allowing single‐step, multi‐level structural control, this new processing concept allows for the chemical modification of the 3D‐printable, phase‐separating preceramic polymer resins using organometallic compounds, including the possibility to generate functional metal nanoparticles in situ during the polymer‐to‐ceramic conversion. In this manner, a chemical toolbox is provided, facilitating the introduction of Ni, Co, Mo, or La into the hierarchically structured SiOC matrix. The versatile applicability of this new materials design approach is demonstrated by employing complex‐shaped, hierarchically porous monoliths containing in situ generated Ni nanoparticles as heterogeneous catalysts for CO2 methanation, with a profound increase in catalyst performance attained by oxidative post‐treatment of the metal‐ceramic hybrid material. [ABSTRACT FROM AUTHOR]

In this study, to enhance protease production, the wild type of Bacillus subtilis E6-5 was mutagenized by random mutagenesis using ultraviolet radiation and ethidium bromide. After combined treatment, several mutants were obtained. Among these mutants, the mutant strain with the largest proteolytic zone diameter (25 mm) was selected and named Bacillus subtilis ATA38. The enzyme production capacity of the obtained mutant was tested and the mutant strain (404 IU/mL at 24 hours) produced 6.7 times more enzyme than the parental strain (60 IU/mL at 32 hours). The effects of some important parameters in the growth medium on enzyme production were examined. The best carbon, organic nitrogen and metal ion were obtained with wheat starch (525 IU/mL), meat extract (850 IU/mL) and KCl+CaCl2 (548 IU/mL), respectively. pH 6.0, 37°C, 200 rpm, inoculum age 18 hours and inoculation amount 1% were obtained as the best physical factors. To further increase the yield, the best nutritional and physical parameters were combined to create a new modified medium. It was determined that the enzyme yield with mutant strain increased 2.7 times in the modified medium (1096 IU/mL) compared to the control (404 U/mL). The mutant strain (1096 IU/mL) showed an 18.2-fold increase in production compared to the wild type (60 IU/mL) in the modified medium. Protease enzyme obtained from ATA38 mutant strain may have great potential in industry for different purposes. [ABSTRACT FROM AUTHOR]

Cancer is one of the leading causes of human death among all major diseases. Metal-based complexes are considered as the most promising vital part in the existing arsenal of cytotoxic candidates used in cancer therapy and diagnostics. The efforts of many scientific groups resulted in the development of numerous metal-based compounds featuring different biologically active organic ligands in order to modulate their bioactivity. Along with the main representatives as potential therapeutic agents, such as the complexes Pt(II)/Pt(IV), Pd(II), Ru(II)/Ru(III), Ag(I), Au(I)/Au(III), Ti(IV), V(IV) and Ga(III), many other transition metal and lanthanide complexes possessing antiproliferative activity are widely discussed in the literature. However, such drugs remain outside the scope of this review. The main purpose of the current study is to review the potential activity of main group metal- and metalloid-based complexes against the most common cancer cell types, such as carcinomas (lung, liver, breast, kidney, gastric, colorectal, bladder, ovarian, cervical, prostate, etc.); sarcomas; blastomas; lymphomas; multiple myeloma; and melanoma. Overcoming the long disregard of organometallic compounds of metals and metalloids from the main groups, a growing number of emerging anticancer agents remarkably prove this field offers an extensive variety of new options for the design of innovative unexplored chemopharmaceutics. Moreover, some of the metal complexes and organometallic compounds from these elements can exhibit entirely different, specific modes of action and biological targets. Obviously, exploitation of their distinct properties deserves more attention. [ABSTRACT FROM AUTHOR]

Additive manufacturing techniques such as vat photopolymerization have laid the foundation for impressive advances in the 3D structuring of ceramic materials. However, simultaneous structuring of these complex‐shaped ceramic objects on the sub‐µm scale, an essential feature for a wide range of applications in separation, energy conversion and storage, adsorption or sensing, has remained a tremendous challenge. This study demonstrates how complex‐shaped polymer‐derived SiOC ceramics exhibiting hierarchical porosity ranging from the sub‐µm‐ to the millimeter‐range can be generated by combining vat photopolymerization with photopolymerization‐induced phase separation using preceramic polymer‐based phase‐separating resins. In addition to allowing single‐step, multi‐level structural control, this new processing concept allows for the chemical modification of the 3D‐printable, phase‐separating preceramic polymer resins using organometallic compounds, including the possibility to generate functional metal nanoparticles in situ during the polymer‐to‐ceramic conversion. In this manner, a chemical toolbox is provided, facilitating the introduction of Ni, Co, Mo, or La into the hierarchically structured SiOC matrix. The versatile applicability of this new materials design approach is demonstrated by employing complex‐shaped, hierarchically porous monoliths containing in situ generated Ni nanoparticles as heterogeneous catalysts for CO2 methanation, with a profound increase in catalyst performance attained by oxidative post‐treatment of the metal‐ceramic hybrid material. [ABSTRACT FROM AUTHOR]

The RuO2-doped organic polymer composite structure was used as the interface to study the photodiode properties of a Schottky structure. Some basic electrical and optoelectrical parameters of the structure interlaid with RuO2:PVC were investigated using the I–V characteristics in the dark and under definite illuminations. The values of saturation current (I0), barrier height (ΦB0) at zero-bias, ideality factor (n), series and shunt resistances (Rs and Rsh) were calculated by using different methods such as thermionic emission, Ohm's law, Cheung and Norde functions. They were found to be intensely depend on illumination levels and voltage. Forward bias I–V data were used to obtain energy-dependent profiles of interface-states (Nss) for each illumination level. Moreover, the open-circuit voltage (Voc), short circuit current (Isc), filling factor (FF), and efficiency (η) of the fabricated Schottky structure were found as 0.118 V, 6.4 μA, 46%, and 0.088% under 50 mW/cm−2, respectively. According to the findings, the RuO2:PVC organic interlayer is light-sensitive and can thus be used in optoelectronic applications, such as photodetectors and photodiodes. [ABSTRACT FROM AUTHOR]

Low-cost and safe batteries are considered to be promising energy-storage systems. Here, a metal organic framework (MOF)-derived octahedral Cu1.95S@CoS2 composite is developed as a high-performance cathode of aluminium-ion (Al-ion) batteries. CoS2 nanoparticles on Cu1.95S provide active sites, making AlCl4− intercalation/deintercalation highly reversible, and reducing polarization. Cycling at 0.5 A g−1, Cu1.95S@CoS2 maintains stable capacities of 136.6 and 122.4 mA h g−1 after 200 cycles at room temperature and −10 °C, respectively. Stable rate-performance is also achieved. These findings will accelerate the application of Al-ion batteries and MOF-derived energy-storage composites. [ABSTRACT FROM AUTHOR]

The reaction of the Ag(I) dimer [Ag2(η2-A)2(μ,η1:η1-A)2][TEF]2 (A = [{CpMo(CO)2}2(μ,η2-P2)]) possessing labile η2-coordinated P2 ligands with the organometallic dipnictogen compounds [{CpMo(CO)2}2(μ,η2-EE′)] (E = E′ = As, Sb; E = P, E′ = As, Sb) represents a facile synthetic route towards unprecedented heteroleptic pnictogen-rich supramolecular complexes. This method can also be extended to the analogous Cu(I) dimer and is studied by DFT computations. [ABSTRACT FROM AUTHOR]

The achievement of significant photoluminescence (PL) in lanthanide ions (Ln3+) has primarily relied on host sensitization, where energy is transferred from the excited host material to the Ln3+ ions. However, this luminous mechanism involves only one optical antenna, namely the host material, which limits the accessibility of excitation wavelength‐dependent (Ex‐De) PL. Consequently, the wider application of Ln3+ ions in light‐emitting devices is hindered. In this study, we present an organic–inorganic compound, (DMA)4LnCl7 (DMA+=[CH3NH2CH3]+, Ln3+=Ce3+, Tb3+), which serves as an independent host lattice material for efficient Ex‐De emission by doping it with trivalent antimony (Sb3+). The pristine (DMA)4LnCl7 compounds exhibit high luminescence, maintaining the characteristic sharp emission bands of Ln3+ and demonstrating a high PL quantum yield of 90–100 %. Upon Sb3+ doping, the compound exhibits noticeable Ex‐De emission with switchable colors. Through a detailed spectral study, we observe that the prominent energy transfer process observed in traditional host‐sensitized systems is absent in these materials. Instead, they exhibit two independent emission centers from Ln3+ and Sb3+, each displaying distinct features in luminous color and radiative lifetime. These findings open up new possibilities for designing Ex‐De emitters based on Ln3+ ions. [ABSTRACT FROM AUTHOR]

The achievement of significant photoluminescence (PL) in lanthanide ions (Ln3+) has primarily relied on host sensitization, where energy is transferred from the excited host material to the Ln3+ ions. However, this luminous mechanism involves only one optical antenna, namely the host material, which limits the accessibility of excitation wavelength‐dependent (Ex‐De) PL. Consequently, the wider application of Ln3+ ions in light‐emitting devices is hindered. In this study, we present an organic–inorganic compound, (DMA)4LnCl7 (DMA+=[CH3NH2CH3]+, Ln3+=Ce3+, Tb3+), which serves as an independent host lattice material for efficient Ex‐De emission by doping it with trivalent antimony (Sb3+). The pristine (DMA)4LnCl7 compounds exhibit high luminescence, maintaining the characteristic sharp emission bands of Ln3+ and demonstrating a high PL quantum yield of 90–100 %. Upon Sb3+ doping, the compound exhibits noticeable Ex‐De emission with switchable colors. Through a detailed spectral study, we observe that the prominent energy transfer process observed in traditional host‐sensitized systems is absent in these materials. Instead, they exhibit two independent emission centers from Ln3+ and Sb3+, each displaying distinct features in luminous color and radiative lifetime. These findings open up new possibilities for designing Ex‐De emitters based on Ln3+ ions. [ABSTRACT FROM AUTHOR]

Directional defects management in polycrystalline perovskite film with inorganic passivator is highly demanded while yet realized for fabricating efficient and stable perovskite solar cells (PSCs). Here, we develop a directional passivation strategy employing a two‐dimensional (2D) material, Cu‐(4‐mercaptophenol) (Cu‐HBT), as a passivator precursor. Cu‐HBT combines the merits of the targeted modification from organic passivator and excellent stability offered by inorganic passivator. Featuring with dense organic functional motifs on its surfaces, Cu‐HBT has the capability to "find" and fasten to the Pb defect sites in perovskites through coordination interactions during a spin‐coating process. During subsequent annealing treatment, the organic functional motifs cleave from Cu‐HBT and convert in situ into p‐type semiconductors, Cu2S and PbS. The resultant Cu2S and PbS not only serve as stable inorganic passivators on the perovskite surface, significantly enhancing cell stability, but also facilitate efficient charge extraction and transport, resulting in an impressive efficiency of up to 23.5 %. This work contributes a new defect management strategy by directionally yielding the stable inorganic passivators for highly efficient and stable PSCs. [ABSTRACT FROM AUTHOR]

Directional defects management in polycrystalline perovskite film with inorganic passivator is highly demanded while yet realized for fabricating efficient and stable perovskite solar cells (PSCs). Here, we develop a directional passivation strategy employing a two‐dimensional (2D) material, Cu‐(4‐mercaptophenol) (Cu‐HBT), as a passivator precursor. Cu‐HBT combines the merits of the targeted modification from organic passivator and excellent stability offered by inorganic passivator. Featuring with dense organic functional motifs on its surfaces, Cu‐HBT has the capability to "find" and fasten to the Pb defect sites in perovskites through coordination interactions during a spin‐coating process. During subsequent annealing treatment, the organic functional motifs cleave from Cu‐HBT and convert in situ into p‐type semiconductors, Cu2S and PbS. The resultant Cu2S and PbS not only serve as stable inorganic passivators on the perovskite surface, significantly enhancing cell stability, but also facilitate efficient charge extraction and transport, resulting in an impressive efficiency of up to 23.5 %. This work contributes a new defect management strategy by directionally yielding the stable inorganic passivators for highly efficient and stable PSCs. [ABSTRACT FROM AUTHOR]

In this study, toxicity of zeolitic metal organic framework-8 nanoparticles on the growth of Escherichia coli, Pseudomonas aeruginosa and Staphylococcus aureus at concentrations of 5–2500 mg/L was assessed. The data were analysed using the Probit analysis and the values of no observed effect concentration (NOEC), lethal concentration-50 (LC50) and 100% bacterial growth inhibition were determined. The minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC) were quantified by micro-dilution method. The 24-h LC50 was 435.24, 327.08 and 76.54 mg/L and NOEC was 147.59, 103.851 and 25.662 mg/L for E. coli, P. aeruginosa and S. aureus, respectively. The 100% growth inhibitory as observed at 2009.093, 1657.094 and 359.833 mg/L, for E. coli, P. aeruginosa and S. aureus, respectively. The lowest MIC and MBC were 12.98 and 26.04 mg/L for S. aureus. This study showed that S. aureus was the suitable indicator due to its high sensitivity to zeolitic metal organic framework-8. [ABSTRACT FROM AUTHOR]

The published data on the substituent influence on the boiling points Tb for 19 series of boron, aluminium, silicon, germanium, tin, and phosphorus compounds were considered using correlation analysis. It was established for the first time that the Tb values depend not only on the classical (inductive, resonance, and steric) effects, but also on the polarizability effect of substituents. In some series, the polarizability effect has a major influence on Tb. [ABSTRACT FROM AUTHOR]

The extraction of U(VI), Th(IV), Am(III), and lanthanides(III) from nitric acid solutions with solutions of phosphorylated pyrazines in organic solvents was studied. The stoichiometry of the extracted complexes was determined, and the influence of the structure of the extractant and an HNO3 concentration in the aqueous phase on the efficiency of the extraction of metal ions into the organic phase was considered. It was established that among the studied compounds, bis(diphenylphosphine)quinoxaline dioxide has the highest extraction ability with respect to actinides and lanthanides in nitric acid media. [ABSTRACT FROM AUTHOR]

Cambridge Structural Database (CSD) is the largest repository of crystal data, containing over 1.2 million crystal structures of organic, metal–organic and organometallic compounds. It is a powerful research tool in many areas, including the extensive studying of noncovalent interactions. In this review, we show how a thorough analysis of CSD crystal data resulted in recognition of novel types of stacking interactions. Even though stacking interactions were traditionally related to aromatic systems, a number of crystallographic studies have shown that nonaromatic metal–chelate rings, as well as hydrogen-bridged rings, can also form stacking interactions. Joined efforts of a CSD analysis and quantum chemical calculations showed that these new stacking interactions are stronger than stacking interactions of aromatic species and recognized them as very important attractive forces in numerous supramolecular systems. [ABSTRACT FROM AUTHOR]

Sustainable water desalination and purification membrane processes require new practical pathways to improve their efficiency. To this end, the inclusion of two-dimensional materials in membrane structure has proven to have a significant impact in various applications. In particular, in processes such as membrane distillation and crystallization, these materials, thanks to their characteristics, help to increase the recovery of clean water and, at the same time, to improve the quality and the production of the recovered salts. Therefore, a fundamental aspect of obtaining 2D materials with certain characteristics is the technique used for the preparation. This review provides a broad discussion on the preparation and proprieties of 2D materials, including examples of organic structures (such as graphene and structures containing transition metals and organic metals). Finally, the critical challenges, future research directions, and the opportunities for developing advanced membranes based on 2D materials are outlined. [ABSTRACT FROM AUTHOR]

A convenient synthesis of [HB(HImMe)3](PF6)2 (ImMe = N-methylimidazolyl) is decribed. This salt serves in situ as a precursor to the tris(imidazolylidenyl)borate Li[HB(ImMe)3] pro-ligand upon deprotonation with nBuLi. Reaction with [W(≡CC6H4Me-4)(CO)2(pic)2(Br)] (pic = 4-picoline) affords the carbyne complex [W(≡CC6H4Me-4)(CO)2{HB(ImMe)3}]. Interrogation of experimental and computational data for this compound allow a ranking of familiar tripodal and facially coordinating ligands according to steric (percentage buried volume) and electronic (νCO) properties. The reaction of [W(≡CC6H4Me-4)(CO)2{HB(ImMe)3}] with [AuCl(SMe2)] affords the heterobimetallic semi-bridging carbyne complex [WAu(μ-CC6H4Me-4)(CO)2(Cl){HB(ImMe)3}]. [ABSTRACT FROM AUTHOR]