Dinuclear Research Articles

Reactions of Ru3(CO)12 with 1,5-bis(diphenylphosphino)pentane: Synthesis, characterization, crystal structure, Hirshfeld surface and QTAIM Analysis of Ru3(CO)10(µ-dpppe)

Reactions of Ru3(CO)12 with 1,5-bis(diphenylphosphino)pentane (dpppe) in THF induced by sodium benzophenone ketyl radical anion, resulted in the expected metal cluster [Ru3(CO)11]2(µ-dpppe) (1) and Ru3(CO)10(µ-dpppe) (2) as the main products. Clusters 1 and 2 were characterized by spectroscopic methods, including Fourier-transform infrared spectroscopy (FTIR) and nuclear magnetic resonance spectroscopy (1H and 31P{1H} NMR).The structural features were determined using single crystal X-ray diffraction analysis. In cluster 1 and 2, the (dpppe) links two trinuclear cluster units via phosphine moieties and bridges to Ru–Ru bond, respectively. Both clusters were stabilized by the presence of C–H⋯O interactions and were further analyzed by Hirshfeld surface analysis. The bonding interactions within cluster 2 were studied using the Quantum Theory of Atoms in Molecules (QTAIM). Various local and integral topological properties of the electron density were calculated, along with the source function (SF) calculations and electron localization function (ELF) analysis.

Distortion Engineering: A Strategy to Modulate Molecular Upconversion with Molecular Cluster-Aggregates.

The rational engineering of molecules is a powerful chemistry tool of pivotal importance in the fields of molecular magnetism and luminescence. Hence, systems that can be modulated via molecular engineering and composition control are expected to present extra versatility regarding the tunability of their properties. This is the case with molecular cluster aggregates (MCAs), high nuclearity molecular compounds. Herein, we demonstrate how the union of both strategies, namely, composition control and molecular engineering, can be employed to enhance molecular upconversion in MCAs. This was achieved by doping a {Gd8Er2Yb10} MCA with CeIII ions. By replacement of the optically silent GdIII ions with CeIII, the upconversion mechanism is modified due to CeIII-mediated cross-relaxation. In addition to this effect, we could also engineer the degree of metal site distortion due to the larger size of CeIII ions, relaxing the selection rules and impacting the upconversion quantum yield and luminescent thermometry. Opto-structural correlations demonstrate that the presented molecular engineering strategy can be used to enhance the performance of molecular upconverters.

Cohesive energy discrepancy drives the fabrication of multimetallic atomically dispersed materials for hydrogen evolution reaction

Atomically dispersed single atom (SA) and atomic cluster (AC) metallic materials attract tremendous attentions in various fields. Expanding monometallic SA and AC to multimetallic SA/AC composites opens vast scientific and technological potentials yet exponentially increasing the synthesis difficulty. Here, we present a general energy-selective-clustering methodology to build the largest reported library of carbon supported bi-/multi-metallic SA/AC materials. The discrepancy in cohesive energy results into selective metal clustering thereby driving the symbiosis of multimetallic SA or/and AC. The library includes 23 bimetallic SA/AC composites, and expanded compositional space of 17 trimetallic, quinary-metallic, septenary-metallic SA/AC composites. We chose bimetallic M1SAM2AC to demonstrate the electrocatalysis utility. Unique decoupled active sites and inter-site synergy lead to 8/47 mV overpotential at 10 mA cm−2 for alkaline/acidic hydrogen evolution and over 1000 h durability in water electrolyzer. Moreover, delicate modulations towards composition and configuration yield high-performance catalysts for multiple electrocatalysis systems. Our work broadens the family of atomically dispersed materials from monometallic to multimetallic and provides a platform to explore the complex composition induced unconventional effects.

Effects of Acid Dissociation and Ionic Solutions on the Aggregation of 2-Pyrone-4,6-dicarboxylic Acid.

The conversion of lignin can produce biomass-derived aromatic compounds such as 2-pyrone-4,6-dicarboxylic acid (PDC), which is a potential sustainable precursor of bioplastics. PDC is a pseudoaromatic dicarboxylic acid that can aggregate in aqueous solution. Aggregation depends upon PDC-PDC, PDC-water, and PDC-ion interactions that are representative of interactions in similar charged, aromatic compounds. These interactions both dictate PDC aggregation and the likelihood that PDC aggregates exhibit parallel stacking configurations that may promote PDC crystallization, which can be leveraged to separate PDC from solution. However, the interplay of interactions that drive aggregation and structure formation, and how these depend upon the charge of PDC and ionic species present in solution, remains unclear. In this work, we investigate PDC aggregation in diverse ionic solutions using all-atom molecular dynamics simulations and molecular clustering analysis. We consider ion-induced dipole interactions by using a modified Lennard-Jones nonbonded model for divalent ions in solutions. From molecular clustering analysis, we derive characteristic parameters to quantify aggregate sizes and parallel stacking configurations. We show that acid dissociation facilitates PDC aggregation in ionic solutions via ion-mediated interactions, and different ionic solutions influence both the likelihood of aggregation and the formation of parallel aggregates. In particular, we find that parallel stacking is primarily found in solutions with monovalent ions, whereas divalent ions promote larger, but less structured, aggregates. These results provide molecular-scale insight into the effects of specific ions on the aggregation of like-charged PDC molecules to inform understanding of related separation processes.

Characterizing m6A modification factors and their interactions in colorectal cancer: implications for tumor subtypes and clinical outcomes

BackgroundThe study aims to comprehensively combine colorectal cancer data cohorts in order to analyze the effects of various DNA methylation-coding genes on colorectal cancer patients. The annual incidence and mortality of colorectal cancer are very high, and there are no effective treatments for advanced colorectal cancer. DNA methylation is a method widely used to regulate epigenetics in the molecular mechanism study of tumors.MethodThree single-cell cohorts GSE166555, GSE146771, and EMTAB8107, and five transcriptome cohorts GSE17536, GSE39582, GSE72970, and TCGA-CRC (TCGA-COAD and TCGA-READ) were applied in this study. 2 erasers (ALKBH5 and FTO), There are 7 writers (METTL3, METTL14, WTAP, VIRMA, RBM15, RBM15B, and ZC3H13) and 11 readers (YTHDC1, IGF2BP1, IGF2BP2, IGF2BP3, YTHDF1, YTHDF3, YTHDC2, and HNRNPA2B1, YTHDF2, HNRNPC and RBMX), a total of 20 M6A regulators, were used as the basis of the dataset in this study and were applied to the construction of molecular typing and prognostic models. Drugs that are differentially sensitive in methylation-regulated gene-related prognostic models were identified using the ConsensusClusterPlus package, which was also used to identify distinct methylation regulatory expression patterns in colorectal cancer and to model the relationship between tissue gene expression profiles and drug IC50 values. Finally, TISCH2 assessed which immune cells were significantly expressed with M6A scores. The immunosuppression of M6A methylation is spatially explained.ResultsThis study used data from 583 CRC patients in the TCGA-CRC cohort. Firstly, the mutation frequency and CNV variation frequency of 20 m6A modification-related factors were analyzed, and the corresponding histogram and heat map were drawn. The study next analyzed the expression variations between mutant and wild forms of the VIRMA gene and explored differences in the expression of these variables in tumor and normal tissues. In addition, the samples were divided into different subgroups by molecular clustering method based on m6A modification, and each subgroup’s expression and clinicopathological characteristics were analyzed. Finally, we compared prognostic differences, tumor microenvironment (TME) characteristics, immune cell infiltration, and gene function enrichment among different subpopulations. We also developed a colorectal cancer m6A-associated gene signature and validated its prognostic effects across multiple cohorts. Finally, using single-cell RNA sequencing data, we confirmed that tumor cells show elevated expression of m6A-related gene signatures.DiscussionThis study explored the mutation frequency, expression differences, interactions, molecular clustering, prognostic effect, and association with tumor characteristics of m6A modification-related factors in CRC and validated them at the single-cell level. These results clarify the association between m6A alteration and colorectal cancer (CRC) and offer important insights into the molecular recognition and management of cancer.

Isomerism in Molecular Metal Carbonyl Clusters

The present microreview focuses on different typologies of isomerism documented along the years for metal carbonyl clusters (MCCs), and outlines their analogies to other classes of ligand‐protected molecular clusters and nanoclusters. Isomerism in molecular MCCs is discussed within two main categories, that is, surface isomerism and core isomerism. The first Section presents some representative examples of surface isomerism involving inorganic (carbonyls and hydrides) and organic ligands, as well as isomerism due to ML fragments decorating the cluster surface. The second Section focuses on three major categories of core isomerism, that is: (1) isomers that mainly differ on M‐M distances; (2) isomers displaying different structures of the metal kernels; (3) isomers possessing almost identical metal kernels and ligand shells, but differing for the positions of different types of metal atoms within the metal kernel. The third Section briefly discusses two related and very rare cases of isomerism, that is, polymerisation and coordination isomerism. General conclusions are outlined in the final Section.

Chemistry of Formate and Water Ligands on Metal Oxide Cluster Nodes of Metal-Organic Framework hcp Hf-UiO-66: Keys to Understanding Reactivity of Paired μ2-OH and Defect Sites.

Many metal-organic frameworks (MOFs) incorporate nodes that are metal oxide clusters, and ligands that have been observed on these nodes include formates, acetates, water, hydroxyl groups, and others, all of which are potentially important in affecting reactivities for applications in separations, catalysis, and sensing. Formate is a common node ligand, arising from formic acid used as a modulator and from N,N-dimethylformamide used as a solvent in MOF syntheses. Yet only little work has been reported characterizing the reactivities of node formate ligands. Infrared spectra reported here show that formate bonds to two types of sites on the paired Hf6O8 nodes of hcp UiO-66, namely, defect and μ2-OH sites. Quantifying the number of formate ligands by 1H NMR spectroscopy of digested samples showed an almost equal number of formate ligands on the two sites, indicating the likelihood that they neighbor each other. These formate ligands interact with water molecules, reversibly switching their bonding from bidentate to monodentate. The formates on μ2-OH sites of hcp Hf-UiO-66 interact much more strongly with water than those on defect sites of the same node, and both interact more strongly than isolated defect sites of Hf-UiO-66. Correspondingly, the catalytic activities of hcp UiO-66 determined as turnover frequencies on each site are approximately twofold higher than those on UiO-66, bolstering the inference that methanol dehydration is catalyzed by a node defect site and a neighboring node μ2-OH site. The results show how MOFs, with their well-defined node structures, provide unprecedented opportunities to understand details of reactivities and catalysis on metal oxide clusters, in contrast to bulk metal oxide surfaces.

Self-sacrificial hydrogen channel enhances the poisoning resistance of ZrCo-based alloy

ZrCo alloy is considered as a promising candidate for hydrogen isotope storage in nuclear fusion reactors. However, severe poisoning caused by the impurities contained in hydrogen is an inevitable issue in engineering applications. Herein, the effects of Cr-doped ZrCo with segregated the reticular ZrCr2 phase on the activation and oxidation resistance were investigated systematically. Experimental results show ZrCo0·95Cr0.05 can achieve 1.71 wt% hydriding capacity within about 37 min under 1 mol% O2 + 99 mol% H2, whereas ZrCo consumes more than 4 times (150 min) to reach the same capacity. Specifically, the improved anti-poisoning ability of the ZrCo–Cr system could be attributed to the three-step chain effect induced by Cr doping, including the hydrogenation-prone and oxygen resistance character of ZrCr2 phases, sacrificial and catalysis of in-situ formed metallic Cr clusters, and protective effects of Cr oxide layers. Hence, the active sites for rapid hydrogen absorption were obtained and inferior oxygen resistance of ZrCo substrates was alleviated through the self-sacrifice of ZrCr2 and Cr. This work not only proves the feasibility of the multi-component alloying strategy in the field of ZrCo alloy anti-poisoning modification, but also reveals that the core of the multi-component alloying strategy is to realize the modulation of the microstructure through the composition design.

Syn-COM: A Multi-Level Predictive Synergy Framework for Innovative Drug Combinations.

Drug prediction and treatment using bioinformatics and large-scale modeling have emerged as pivotal research areas. This study proposes a novel multi-level collaboration framework named Syn-COM for feature extraction and data integration of diseases and drugs. The framework aims to explore optimal drug combinations and interactions by integrating molecular virtuality, similarity clustering, overlap area, and network distance. It uniquely combines the characteristics of Chinese herbal medicine with clinical experience and innovatively assesses drug interaction and correlation through a synergy matrix. Gouty arthritis (GA) was used as a case study to validate the framework's reliability, leading to the identification of an effective drug combination for GA treatment, comprising Tamaricis Cacumen (Si = 0.73), Cuscutae Semen (Si = 0.68), Artemisiae Annuae Herba (Si = 0.62), Schizonepetae Herba (Si = 0.73), Gleditsiae Spina (Si = 0.89), Prunellae Spica (Si = 0.75), and Achyranthis Bidentatae Radix (Si = 0.62). The efficacy of the identified drug combination was confirmed through animal experiments and traditional Chinese medicine (TCM) component analysis. Results demonstrated significant reductions in the blood inflammatory factors IL1A, IL6, and uric acid, as well as downregulation of TGFB1, PTGS2, and MMP3 expression (p < 0.05), along with improvements in ankle joint swelling in GA mice. This drug combination notably enhances therapeutic outcomes in GA by targeting key genes, underscoring the potential of integrating traditional medicine with modern bioinformatics for effective disease treatment.

Controlling the Size of Molecular Copper Clusters Supported by a Multinucleating Macrocycle.

The use of a nonrigid, pyridyldialdimine-derived macrocyclic ligand (3PDAI2) enabled the synthesis of well-defined mono-, di-, tri-, and tetra-nuclear Cu(I) complexes in good yields through rational synthetic means. Starting from mono- and diargentous 3PDAI2 complexes, transmetalation to Cu(I) proceeded smoothly with formation of AgX (X = Cl, I) salts to generate mono-, di-, and trinuclear copper complexes. Monodentate supporting ligands (MeCN, xylNC, PMe3, PPh3) were found to either transmetallate with or bind various di- and trinuclear clusters. The solution-phase dynamic behaviors of these species were studied through NMR spectroscopic investigations, and an in-depth study of the trinuclear systems revealed a rate dependence on the identity of the supporting ligand, indicating that ligand dissociation reactions were involved in the dynamic exchange processes. Synthetic investigations further found methods for the purposeful interconversion between the di- and trinuclear systems as well as the synthesis of a pseudotetrahedral tetracopper complex with two μ-Ph supporting ligands.

Understanding the atomistic behavior of small molecules (O2 and N2) on monometallic M13 nanoparticles

Both experimental data and density functional theory (DFT) calculations clearly indicate that the reactivity of metal clusters for NO is determined by the energy and orbital type (4d or 5s) of the valence band top. Here, we explore this correlation for the reactivity of M13 nanoclusters, being M = Ag, Au, Co, Cu, Fe, Ir, Ni, Os, Pd, Pt, Rh and Ru and adsorbed diatomic molecules, O2 or N2. The possible adsorption configurations, interatomic distances, and adsorption energies for O2 and N2 on M13 clusters have been analyzed in detail.

Four novel coordination polymers with beautiful three-dimensional frameworks as potential Fe3+/Cr2O72− sensors

Protecting water resources is the innate obligation of human beings, and detecting pollutants in water is an important work to protect water resources. In this work, we have prepared four novel coordination polymers, named {[Zn3(L)2(H2O)4]‧5H2O}n (1), {[Zn6(L)4(4,4′-bpy)(H2O)6]‧3H2O}n (2), [Cd(HL)(H2O)]n (3) and [Cd3(L)2(pyz)(H2O)3]n (4) (H3L = 1-(3-carboxybenzyl)-1H-pyrazole-3,5-dicarboxylic acid, 4,4′-bpy = 4,4′-bipyridine and pyz = pyrazine). The organic ligands exhibit various coordination patterns, making the beautiful structures of the four compounds quite different. Compounds 1, 2, and 4 all show three core clusters and form the final three-dimensional frameworks by interconnecting metal clusters and organic ligands. Meanwhile, compound 3 displays the infinite metal chain and forms the final three-dimensional framework. These four compounds were also used to detect cations/anions in the water, showing that they can selectively detect Fe3+ and Cr2O72−. The excellent anti-interference ability, limit of detection, and reproducibility suggest that these four compounds are all potential sensing materials for Fe3+ and Cr2O72−.

Thermodynamic origin of the affinity, selectivity, and domain specificity of metallothionein for essential and toxic metal ions.

The small Cys-rich protein metallothionein (MT) binds several metal ions in clusters within two domains. While the affinity of MT for both toxic and essential metals has been well studied, the thermodynamics of this binding has not. We have used isothermal titration calorimetry measurements to quantify the change in enthalpy (ΔH) and change in entropy (ΔS) when metal ions bind to the two ubiquitous isoforms of MT. The seven Zn2+ that bind sequentially at pH 7.4 do so in two populations with different coordination thermodynamics, an initial four that bind randomly with individual tetra-thiolate coordination and a subsequent three that bind with bridging thiolate coordination to assemble the metal clusters. The high affinity of MT for both populations is due to a very favourable binding entropy that far outweighs an unfavourable binding enthalpy. This originates from a net enthalpic penalty for Zn2+ displacement of protons from the Cys thiols and a favourable entropic contribution from the displaced protons. The thermodynamics of other metal ions binding to MT were determined by their displacement of Zn2+ from Zn7MT and subtraction of the Zn2+-binding thermodynamics. Toxic Cd2+, Pb2+, and Ag+, and essential Cu+, also bind to MT with a very favourable binding entropy but a net binding enthalpy that becomes increasingly favourable as the metal ion becomes a softer Lewis acid. These thermodynamics are the origin of the high affinity, selectivity, and domain specificity of MT for these metal ions and the molecular basis for their in vivo binding competition.

Orbital magnetism through inverse Faraday effect in metal clusters

Abstract In view of the recent increased interest in light-induced manipulation of magnetism in nanometric length scales this work presents metal clusters as promising elementary units for generating all-optical ultrafast magnetization. We perform a theoretical study of the opto-magnetic properties of metal clusters through ab-initio real-time (RT) simulations in real-space using time-dependent density functional theory (TDDFT). Through ab-initio calculations of plasmon excitation with circularly polarized laser pulse in atomically precise clusters of simple and noble metals, we discuss the generation of orbital magnetic moments due to the transfer of angular momentum from light field through optical absorption at resonance energies. Notably, in the near-field analysis we observe self-sustained circular motion of the induced electron density corroborating the presence of nanometric current loops which give rise to orbital magnetic moments due to the inverse Faraday effect (IFE) in the clusters. The results provide valuable insights into the quantum many-body effects that influence the IFE-mediated light-induced orbital magnetism in metal clusters depending on its geometry and chemical composition. At the same time, they explicitly demonstrate the possibility for harnessing magnetization in metal clusters, offering potential applications in the field of all-optical manipulation of magnetism.

Molecular cluster, transmission characteristics, origin and dynamics analysis of HIV-1 CRF59_01B in China: A molecular epidemiology study

PurposeThis study investigated for the HIV-1 CRF59_01B epidemic's spatiotemporal dynamics and its transmission networks in China. MethodsBetween 2007 and 2020, a total of 250 partial pol gene sequences of HIV-1 CRF59_01B were collected from four regions (10 Chinese provinces). Phylogenetic tree construction and cluster identification were then performed. The Bayesian skyline and birth–death susceptible–infected–removed models were employed for the phylodynamic analyses of subtypes and large clusters, respectively. Phylogenetic analyses and trait diffusion of these sequences were performed using Bayesian phylogenetic methods (beast-classic package). Distance-based molecular network analyses were performed to identify putative relationships. ResultsUsing a genetic distance threshold of 1.3 %, We identified 45 clusters that included 62.40 % (156/250) of the sequences. Three clusters (6.67 %, 3/45) had 10 or more sequences, and were considered "large clusters". Six clusters (13.33 %) included sequences from different regions (Southeast, Northeast, Southeast, and Central China). Thirteen clusters (28.89 %) included sequences of men who had sex with men only, three clusters (6.67 %) included sequences of heterosexuals only, and 12 clusters (26.67 %) included sequences of both groups. The substitution rate of CRF59_01B was 1.91 × 10–3 substitutions per site per year [95 % highest posterior density (HPD) interval: 1.39 × 10−3–2.49 × 10−3)], the time to the most recent common ancestor of CRF59_01B was to be 1992.83 (95 % HPD: 1977.97–2002.81). A Bayesian skyline plot revealed that the effective population size of CRF59_01B increased from 2000 to 2015 and remained stable after 2015. The large clusters showed continuous growth from 2013 to 2020. Phylogeographic analysis showed that CRF59_01B B most likely originated in Southeast China, with a posterior probability of 97.44 %, and then spread to other regions. ConclusionsOur study revealed the temporal and geographical origins of HIV-1 CRF59_01B as well as the process of transmission among various regions and risk groups in China, which can help develop targeted HIV prevention strategies.

PANoptosis-related molecular clustering and prognostic signature associated with the immune landscape and therapy response in breast cancer.

Breast cancer (BC) remains one of the most pervasive and complex malignancies. PANoptosis represents a recently identified cellular mechanism leading to programmed cell death. However, the prognostic implications and influence on the immune microenvironment of BC pertaining to PANoptosis-related genes (PRGs) remain significantly understudied. We conducted differential expression analysis to identify prognostic-Related PRGs by the Cancer Genome Atlas (TCGA) and the Gene Expression Omnibus (GEO) databases. Next, we identified the PANoptosis-related molecular subtype using the consensus clustering analysis, and constructed and validated the PANoptosis-related prognostic signature using LASSO and Cox regression analyses. ROC curves were employed to assess the performance of the signatures. Furthermore, drug sensitivity between low- and high-risk group were analysis. Finally, we conducted RT-qPCR to assess the gene expression levels involved in this signature. We categorized BC patients into 2 distinct molecular clusters based on PRGs and identified differentially expressed genes associated with prognosis. Subsequently, BC patients were then divided into 2 gene clusters. The identified PRGs molecular clusters and gene clusters demonstrated association with patient survival, immune system functions, and biological processes and pathways of BC. A prognostic signature comprising 5 genes was established, and BC patients were classified into low- and high-risk groups based on the risk scores. The ROC curves demonstrated that those in the low-risk category exhibited notably extended survival compared to the high-risk group. A nomogram model for patient survival was constructed based on the risk score in conjunction with other clinical features. High-risk group had higher tumor burden mutation, CSC index and lower StomalScore, ImmuneScore, and ESTIMATEScore. Subsequently, we established a correlation between the risk score and drug sensitivity among BC patients. Finally, qRT-PCR results showed that the expression of CXCL1, PIGR, and TNFRSF14 significantly decreased, while CXCL13 and NKAIN were significantly increased in BC tissues. We have developed a molecular clustering and prognostic signature based on PANoptosis to improve the prediction of BC prognosis. This discovery has the potential to not only assist in assessing overall patient prognosis but also to deepen our understanding of the underlying mechanisms of PANoptosis in BC pathogenesis.

Improvement of seismic performance of concrete structures using magnetized concrete: an empirical study

High-Performance Concrete (HPC) offers better workability, compressive strength, and durability compared to ordinary concrete. One type of high-strength concrete is magnetic concrete. The primary objective of this empirical research is to investigate the potential of magnetized concrete in enhancing the seismic properties of concrete structures, in this technology, the physical structure of water is altered by inducing a magnetic field. The research employs empirical methods, including experimental testing and analysis, to assess the seismic performance of magnetized concrete compared to traditional concrete. As a result, the number of molecules in a molecular cluster decrease from 13 to 5 or 6, and the surface tension of the water is reduced. Using this water in concrete preparation increases the workability of the concrete mix and reduces the required water. Additionally, by facilitating cement hydration, it increases the compressive strength and durability of the concrete. This increased compressive strength enhances the stability and resistance of the structure against earthquake forces. Moreover, maintaining the compressive strength of the concrete while using magnetic water can reduce cement consumption. This reduction in cement consumption can lower the weight of the structure, which is very effective in reducing earthquake forces in tall buildings.

Complex Phase Transitions of Fully Rigid Sphere-Rod Amphiphiles Induced by Solvent Polarity in Dilute Solutions.

We report complex macrophase and microphase transitions of rigid amphiphiles with spherical Keggin molecular clusters as the solvophilic block and rod-like rigid oligofluorene (OF) as the solvophobic block in mixed solvents of water and polar organic solvent. By properly adjusting the solvent polarity, the amphiphiles are found to respond accordingly by self-assembling into multilayered incomplete onion-like structures (10-25 vol % THF), single-layered vesicular structures (60 vol % THF), and an unexpected macrophase separation in the middle (40-50 vol % THF), which is due to the anomalous trends in Keggin solubility as a result of the nature of TBA+ counterions. The rigidity of the OF block prevents the amphiphile from assembling by following the rule of packing parameters; instead, interdigitation among different rods leads to the formation of the solvophobic domain to achieve self-assembly. The incomplete onion structures are controlled by the interdigitation of rigid rods for the number of layers and the electrostatic interaction among Keggin head groups for the interlayer distance. When the degree of interdigitation becomes lower, the self-assembly process shows a trend that can be explained by the traditional rule of packing parameter. This study demonstrates the formation of different self-assembled structures by rigid amphiphiles and their transitions induced by solvent composition. The self-assembly (microphase separation) of rigid amphiphiles in a dilute solution could indeed represent a broad area containing complicated, uncharted rules.

Dative Bonding Activation Enables Precise Functionalization of the Remote B-H Bond of nido-Carborane Clusters.

The innovation of synthetic strategies for selective B-H functionalization is a pivotal objective in the realm of boron cluster chemistry. However, the precise, efficient, and rapid functionalization of a B-H bond of carboranes that is distant from the existing functional groups remains intractable owing to the limited approaches for site-selective control from the established methods. Herein, we report a dative bonding activation strategy for the selective functionalization of a nonclassical remote B-H site of nido-carboranes. By leveraging the electronic effects brought by the exopolyhedral B(9)-dative bond, a cross-nucleophile B-H/S-H coupling protocol of the distal B(5)-H bond has been established. The dative bond not only amplifies the subtle reactivity difference among B-H bonds but also significantly changes the reactive sites, further infusing nido-carboranes with additional structural diversity. This reaction paradigm features mild conditions, rapid conversion, efficient production, broad scope, and excellent group tolerance, thus enabling the applicability to an array of complex bioactive molecules. The efficient and scalable reaction platform is amenable to the modular construction of photofunctional molecules and boron delivery agents for boron neutron capture therapy. This work not only provides an unprecedented solution for the selective diversification of distal B-H sites in nido-carboranes but also holds the potential for expediting the discovery of novel carborane-based functional molecules.

Stability and Dynamics of Zeolite-Confined Gold Nanoclusters.

Nanoengineered metal@zeolite materials have recently emerged as a promising class of catalysts for several industrially relevant reactions. These materials, which consist of small transition metal nanoclusters confined within three-dimensional zeolite pores, are interesting because they show higher stability and better sintering resistance under reaction conditions. While several such hybrid catalysts have been reported experimentally, key questions such as the impact of the zeolite frameworks on the properties of the metal clusters are not well understood. To address such knowledge gaps, in this study, we report a robust and transferable machine learning-based potential (MLP) that is capable of describing the structure, stability, and dynamics of zeolite-confined gold nanoclusters. Specifically, we show that the resulting MLP maintains ab initio accuracy across a range of temperatures (300-1000 K) and can be used to investigate time scales (>10 ns), length scales (ca. 10,000 atoms), and phenomena (e.g., ensemble-averaged stability and diffusivity) that are typically inaccessible using density functional theory (DFT). Taken together, this study represents an important step in enabling the rational theory-guided design of metal@zeolite catalysts.