Solvent Molecules Research Articles

Toward a numerically efficient description of bulk-solvated anionic states.

We investigate the vertical electron attachment energy (VAE) of 1-methyl-4-nitroimidazole, a model radiosensitizer, employing quantum mechanics/molecular mechanics (QM/MM) and QM/polarized continuum (QM/PCM) solvation models. We considered the solvent-excluded surface (QM/PCM-SES) and Van der Waals (QM/PCM-VDW) cavities within the PCM framework, the electrostatic embedding QM/MM (EE-QM/MM) model, and the self-consistent sequential QM/MM polarizable electrostatic embedding (scPEE-S-QM/MM) model. Due to slow VAE convergence concerning the number of QM solvent molecules, full QM calculations prove inefficient. Ensemble averages in these calculations do not align with VAEs computed for the representative solute-solvent configuration. QM/MM and QM/PCM calculations show agreement with each other for sufficiently large QM regions, although the QM/PCM-VDW model exhibits artifacts linked to the cavity. QM/MM models demonstrate good agreement between ensemble averages and VAEs calculated with the representative configuration. Notably, the VAE computed with the scPEE-S-QM/MM model achieves faster convergence concerning the number of QM water molecules compared to the EE-QM/MM model, attributed to enhanced efficiency from MM charge polarization in the scPEE-S-QM/MM approach. This emphasizes the importance of QM/classical models with accurate solute-solvent and solvent-solvent mutual polarization for obtaining converged VAEs at a reasonable computational cost. The full-QM approach is very inefficient, while the microsolvation model is inaccurate. Computational savings in QM/MM models result from electrostatic embedding and the representative configuration, with the scPEE-S-QM/MM approach emerging as an efficient tool for describing bulk-solvated anions within the QM/MM framework. Its potential extends to improving transient anion state descriptions in biomolecules and radiosensitizers, especially given the frequent employment of microsolvation models.

Ion transport mechanisms in covalent organic frameworks: implications for technology.

Covalent organic frameworks (COFs) have emerged as promising materials for ion conduction due to their highly tunable structures and excellent electrochemical stability. This review paper explores the mechanisms of ion conduction in COFs, focusing on how these materials facilitate ion transport across their ordered structures, which is crucial for applications such as solid electrolytes in batteries and fuel cells. We discuss the design strategies employed to enhance ion conductivity, including pore size optimization, functionalization with ionic groups, and the incorporation of solvent molecules and salts. Additionally, we examine the various applications of ion-conductive COFs, particularly in energy storage and conversion technologies, highlighting recent advancements and future directions in this field. This review paper aims to provide a comprehensive overview of the current state of research on ion-conductive COFs, offering insights into their potential to design highly ion-conductive COFs considering not only fundamental studies but also practical perspectives for advanced electrochemical devices.

Aggregative Luminescence from CsPbBr3 Perovskite Precursors

AbstractUnderstanding the properties of the precursor can provide deeper insight into the crystallization and nucleation mechanisms of perovskites, which is vital for the solution‐process device performance. Herein, we conducted a detailed investigation into the photophysics properties of CsPbBr3 precursors in a broad concentration and various solvents. The precursor transformed from the solution state into the colloidal state and exhibited aggregation‐induced emission character as the concentration increased. The aggregative luminescence from the precursors originates from the polybromide plumbous that is formed through the coordination of solvent molecules to the lead metal center. Two adducts with monodentate (PbBr2 ⋅ solvent) and bidentate (PbBr2 ⋅ 2solvent) ligands can be obtained, accompanied by emission with photoluminescence at 610 and 565 nm, respectively. Furthermore, the aggregative luminescence intensity and color could be regulated by changing the solvent and precursor ratio. Besides, we discussed the difference between the molecular aggregate in the organic system and the ionic aggregate in the inorganic system: the ionic aggregate is composed of solvated ions rather than individual molecules as in organic systems, which could possess properties that ions do not have. The fluorescence that is sensitive to Pb2+ coordination reported here could be applied to screen perovskite additives and judge the precursor aging.

Aggregative Luminescence from CsPbBr3 Perovskite Precursors.

Understanding the properties of the precursor can provide deeper insight into the crystallization and nucleation mechanisms of perovskites, which is vital for the solution-process device performance. Herein, we conducted a detailed investigation into the photophysics properties of CsPbBr3 precursors in a broad concentration and various solvents. The precursor transformed from the solution state into the colloidal state and exhibited aggregation-induced emission character as the concentration increased. The aggregative luminescence from the precursors originates from the polybromide plumbous that is formed through the coordination of solvent molecules to the lead metal center. Two adducts with monodentate (PbBr2 ⋅ solvent) and bidentate (PbBr2 ⋅ 2solvent) ligands can be obtained, accompanied by emission with photoluminescence at 610 and 565 nm, respectively. Furthermore, the aggregative luminescence intensity and color could be regulated by changing the solvent and precursor ratio. Besides, we discussed the difference between the molecular aggregate in the organic system and the ionic aggregate in the inorganic system: the ionic aggregate is composed of solvated ions rather than individual molecules as in organic systems, which could possess properties that ions do not have. The fluorescence that is sensitive to Pb2+ coordination reported here could be applied to screen perovskite additives and judge the precursor aging.

Evaluating the Impact of Sonication Process on Graphene Oxide Structural Properties

Graphene oxide (GO) is one of the members of carbon-based nanomaterials and can be featured as graphene structure decorated with various oxygenated functional groups. Recently, various methods have been found for producing carbon-based nanomaterials with enhanced efficiency in several applications. The chemical process involves oxidizing graphite to GO using a powerful oxidizing chemical. Hummers method is one of the most known and versatile method for the production of GO nanomaterials because of its ease of application, parameter controllability and high yield. This process enables graphite oxidation and exfoliation into single- or multi-layered GO sheets. Exfoliation, the separation of graphene or graphitic layers, is a critical process in GO synthesis. Since exfoliation separates multilayered graphite oxide flakes or particles, it forms single layer GO by forcing oxidizing agents or solvent molecules between layers. The sonication process can exfoliate the oxidized layers, resulting in the formation of GO structure when the exfoliated layers consist of only one or a few layers of carbon atoms. Therefore, sonication procedure is among the key parameters of Hummers method that influences the characteristics of GO-based nanomaterials. In this study, the impact of sonication duration time and power parameters on morphological and structural characteristics of GO development was examined. For this purpose, characterization studies were performed by using Scanning electron microscope (SEM), X-ray powder diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), UV-Vis spectroscopy and Raman spectroscopy analysis. The findings revealed that the increase in sonication power and time led to an increase in defects in the resulting GO structure.

A First-Principles Study on the Anchoring Properties of Defective Single-Walled Carbon Nanotubes for Lithium-Sulfur Batteries

Abstract The application of lithium-sulfur (Li-S) batteries is impeded by the significant polysulfide shuttling phenomenon. Developing suitable anchoring material is an effective way to restrain this behavior. In this work, the anchoring performance of lithium polysulfide (LiPSs) on defective single-wall carbon nanotubes (DSWNT) is investigated by density functional theory. The results demonstrate that the DSWNT with three carbon vacancies (DSWNT-3) has the highest forming capacity and the strongest adsorption capacity, indicating it has the best anchoring effect of LiPSs. As the anchoring material of the cathode, DSWNT-3 has greater energy than solvent molecules to inhibit the dissolution of long-chain polysulfides. In general, DSWNT-3 demonstrates notable efficacy as an anchoring material for Li-S batteries, which establishes a theoretical foundation for exploring the anchoring characteristics of defects and their application in the cathode of Li-S batteries.

Selection of organic solvents as reaction media for laccase from Trametes versicolor

The ability of laccases to work effectively in properly selected aqueous-organic solutions significantly expands the scope of their application, making them commercially attractive and more competitive. However, it must be considered that molecules of organic solvent are very aggressive towards enzymes and destroy weak non-covalent interactions that maintain the spatial structure of the protein. In this work, we quantitatively described the influence of the nature of water-miscible organic solvents and their concentration on the activity and stability of Trametes versicolor laccase during the oxidation of ABTS (2,2-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid)) through the maximum rates and the Michaelis constants KM. The obtained kinetic parameters make it possible to compare the effect of various organic solvents on laccase and select the most optimal one, which minimizes the decrease in enzyme activity, maintains its stability and allows repeated use. Among the solvents studied, polyhydroxy compounds have the least negative effect on laccase activity; however, in all cases, a high concentration of organic solvent (≥30% (v/v)) leads to suppression of enzymatic activity. It has been shown that the longer the alkyl chain (hydrophobic fragment of the structure), the stronger the negative effect of alcohols on enzymes. The most toxic solvent for Trametes versicolor laccase is isopropanol. In addition, numerous examples of various uses of Trametes versicolor in aquatic-organic environments are discussed here.

THF-Assisted CO2 Reduction Catalyzed by Electride Mg2EP: Insight from DFT Calculations.

Hydroboration and hydrogenation reductions of CO2 catalyzed by a porphyrinoid-based dimagnesium(I) electride (Mg2EP) were investigated by density functional theory calculations. Herein, the presence of potentially excess electrons located at the Mg-Mg bond endows Mg2EP with the ability to activate small molecules such as CO2, HBpin, and H2, thus opening up the possibility for further CO2 conversion. The Mg2EP-catalyzed hydroboration of CO2 to HCOOBpin is predicted to have relatively higher activity in comparison to the hydrogenation reduction to formic acid (HCOOH). Interestingly, the common solvent molecule tetrahydrofuran as an auxiliary can coordinate with the Mg center to effectively weaken the bonding interaction between the dimagnesium center and the intermediate species from the CO2 conversion, thereby promoting the catalytic cycle for the CO2 hydroboration. The present results suggest that the electride Mg2EP is promising for the molecular catalyst in the CO2 transformation.

Single Crystal to Single Crystal Transformation of Porous Materials based on Zinc Nodes and Mercaptobenzoic Acid.

Porous coordination polymers (PCPs) are an excellent class of porous crystalline materials with tunable properties and intriguing potential applications spanning multiple disciplines. In this work, we report the synthesis and characterization of a PCP (HI-103) based on 4,4'-dithiodibenzoic acid ligand and zinc nitrate with two DMF molecules residing in the porous network. The stability of the porous network was analyzed by heating the compound at 60.0 °C for two days, and the structural analysis revealed a new PCP (HI-104) was formed with one of the DMF molecules, indicating a single-crystal to single-crystal (SCSC) transformation. The solvent molecules were completely removed by extensive drying (HI-103-dry), and the integrity of the porous network was verified by powder X-ray diffraction (PXRD) and thermogravimetric analysis. The reversibility of SCSC transformation was confirmed by treating HI-103-dry with DMF molecules, resulting in HI-103 after five days. The adsorption studies of HI-103-dry with other solvents revealed that SCSC transformation was not observed for DMA and DEA, but some structural changes were observed in the presence of DMSO. The adsorption studies performed in the presence of an equimolar mixture of DMF, DMA, and DMA indicated that HI-103-dry could selectively adsorb DMF molecules from the analogous mixture.

AttenGpKa: A Universal Predictor of Solvation Acidity Using Graph Neural Network and Molecular Topology.

Rapid and accurate calculation of acid dissociation constant (pKa) is crucial for designing chemical synthesis routes, optimizing catalysts, and predicting chemical behavior. Despite recent progress in machine learning, predicting solvation acidity, especially in nonaqueous solvents, remains challenging due to limited experimental data. This challenge arises from treating experimental values in different solvents as distinct data domains and modeling them separately. In this work, we treat both the solutes and solvents equally from a perspective of molecular topology and propose a highly universal framework called AttenGpKa for predicting solvation acidity. AttenGpKa is trained using 26,522 experimental pKa values from 60 pure and mixed solvents in the iBonD database. As a result, our model can simultaneously predict the pKa values of a compound in various solvents, including pure water, pure nonaqueous, and mixed solvents. AttenGpKa achieves universality by using graph neural networks and attention mechanisms to learn complex effects within solute and solvent molecules. Furthermore, encodings of both solute and solvent molecules are adaptively fused to simulate the influence of the solvent on acid dissociation. AttenGpKa demonstrates robust generalization in extensive validations. The interpretability studies further indicate that our model has effectively learnt electronic and solvent effects. A free-to-use software is provided to facilitate the use of AttenGpKa for pKa prediction.

AttenGpKa: A Universal Predictor of Solvation Acidity Using Graph Neural Network and Molecular Topology.

Rapid and accurate calculation of acid dissociation constant (pKa) is crucial for designing chemical synthesis routes, optimizing catalysts, and predicting chemical behavior. Despite recent progress in machine learning, predicting solvation acidity, especially in nonaqueous solvents, remains challenging due to limited experimental data. This challenge arises from treating experimental values in different solvents as distinct data domains and modeling them separately. In this work, we treat both the solutes and solvents equally from a perspective of molecular topology and propose a highly universal framework called AttenGpKa for predicting solvation acidity. AttenGpKa is trained using 26,522 experimental pKa values from 60 pure and mixed solvents in the iBonD database. As a result, our model can simultaneously predict the pKa values of a compound in various solvents, including pure water, pure nonaqueous, and mixed solvents. AttenGpKa achieves universality by using graph neural networks and attention mechanisms to learn complex effects within solute and solvent molecules. Furthermore, encodings of both solute and solvent molecules are adaptively fused to simulate the influence of the solvent on acid dissociation. AttenGpKa demonstrates robust generalization in extensive validations. The interpretability studies further indicate that our model has effectively learnt electronic and solvent effects. A free-to-use software is provided to facilitate the use of AttenGpKa for pKa prediction.

Co/Ni/Cu-NH2BDC MOF@natural Egyptian zeolite ore nanocomposite for calcium ion removal in water softening applications.

Water softening is a treatment process required to remove calcium (Ca(II)) and magnesium (Mg(II)) cations from water streams. Nanocomposites can provide solutions for such multiple challenges and have high performance and low application costs. In this work, a multimetallic cobalt, nickel, and copper 2-aminoterephthalic acid metal-organic framework ((Co/Ni/Cu-NH2BDC) MOF) was synthesized by a simple solvothermal technique. This MOF was supported on an Egyptian natural zeolite ore and was used for the adsorption of Ca(II) ions for water-softening applications. The adsorbent was characterized using Fourier transform infrared (FTIR) spectroscopy, field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), N2 adsorption-desorption isotherms, and zeta potential measurements. The adsorption isotherm data for the prepared adsorbent toward Ca(II) were best fit using the Redlich-Peterson model and showed a maximum adsorption capacity of 88.1 mg/g. The adsorption kinetics revealed an equilibrium time of 10 min, which was best fit using the Avrami model. The intermolecular interactions of Ca(II) ions with zeolite and MOF were investigated by Monte Carlo simulations, molecular dynamics simulations, and FTIR and XRD analyses. The adsorption sites in the zeolite structure were oxygen atoms, while those in the MOF structure were amine nitrogen atoms. The Ca(II) ions are coordinated with the solvent molecules in both structures. Finally, the in vitro cytotoxicity of this nanocomposite was assessed, revealing viability levels of 74.57 ± 2.1% and 21 ± 2.79% for Vero and African green monkey kidney and human liver (HepG2) cells, respectively. Cytotoxicity assays help assess the environmental impact of these materials, ensuring that they do not harm aquatic organisms or disrupt ecosystems. Thus, this study demonstrated the valorization of MOF/zeolite as a valuable and industry-ready adsorbent that can appropriate Ca(II) contaminants from aqueous streams.

Chiral Solvent-Induced Homochiral Hierarchical Molecular Assemblies at the Liquid/Solid Interface.

We herein investigate the formation of homochiral hierarchical self-assembled molecular networks (SAMNs) via chirality induction by the coadsorption of a chiral solvent at the liquid/graphite interface by means of scanning tunneling microscopy (STM). In a mixture of achiral solvents, 1-hexanoic acid, and 1,2,4-trichlorobenzene, an achiral dehydrobenzo[12]annulene (DBA) derivative with three alkoxy and three hydroxy groups in an alternating manner forms chiral hierarchical triangular cluster structures through dynamic self-sorting. Enantiomorphous domains appear in equal probability. On the other hand, in chiral 2-methyl-1-hexanoic acid as a solvent, this molecule produces (i) homochiral small triangular clusters at a low solute concentration, (ii) a chirality-biased hierarchical structure consisting of triangular cluster structures with different cluster sizes at a medium concentration, and (iii) a dense structure with no chirality bias at a high concentration. We attribute the concentration-dependent degree of the chirality transmission to the number of coadsorbed solvent molecules in the SAMNs and to the difference in nucleus structure and size in the initial stage of the SAMN formation.

UoC‐11: An Interpenetrating MOF from Fluorinated BTB Ligands and a 1‐D Mg Based SBU

A new MOF, named UoC‐11 (UoC = University of Cologne, [Mg4(3F‐BTB)2(OAc)2(DMF)6] · DMF), based on a fluorinated BTB (4,4′,4″‐benzene‐1,3,5‐triyl‐tris‐(benzoate)) derivative and Mg cations was synthesized incorporating additional acetate anions. Its crystal structure was determined from single crystal X‐ray diffraction data (P21/c, Z = 4). It consists of one‐dimensional Mg‐SBUs (strands), interconnected perpendicularly by tritopic linkers forming a dense two‐fold interpenetrating 3D network. Thus, only very small voids are formed which are fully occupied by the solvent. After activation at 150 °C (24 hours), no meaningful N2 adsorption was observed. Compared to the Ca and Sr analogues UoC‐9, UoC‐11 does not exhibit a crystal sponge behaviour. Thermal analysis (TGA) shows a release of all solvent molecules up to ~280 °C and the decomposition of the framework starts above 300 °C.

UoC‐11: An Interpenetrating MOF from Fluorinated BTB Ligands and a 1‐D Mg Based SBU

A new MOF, named UoC‐11 (UoC = University of Cologne, [Mg4(3F‐BTB)2(OAc)2(DMF)6] · DMF), based on a fluorinated BTB (4,4′,4″‐benzene‐1,3,5‐triyl‐tris‐(benzoate)) derivative and Mg cations was synthesized incorporating additional acetate anions. Its crystal structure was determined from single crystal X‐ray diffraction data (P21/c, Z = 4). It consists of one‐dimensional Mg‐SBUs (strands), interconnected perpendicularly by tritopic linkers forming a dense two‐fold interpenetrating 3D network. Thus, only very small voids are formed which are fully occupied by the solvent. After activation at 150 °C (24 hours), no meaningful N2 adsorption was observed. Compared to the Ca and Sr analogues UoC‐9, UoC‐11 does not exhibit a crystal sponge behaviour. Thermal analysis (TGA) shows a release of all solvent molecules up to ~280 °C and the decomposition of the framework starts above 300 °C.

Adsorption of Prochiral Solvent Molecules by Surface-Confined Chiral Supramolecular Assemblies: How Solvent Impacts On-Surface Chirality.

The understanding of supramolecular chirality in self-assembled molecular networks (SAMNs) on surfaces generates a lot of interest because of its relation to the production of chiral sensors, reactors, and catalysts. We herein report the adsorption of a prochiral solvent molecule in porous SAMNs formed by a chiral dehydrobenzo[12]annulene (cDBA) derivative. Through the prochirality recognition of a solvent molecule, the supramolecular chirality of the SAMN is switched: the cDBA exclusively forms a counter-clockwise pore through co-adsorption of the solvent molecule in prochiral 1,2,4-trichlorobenzene, while in 1-phenyloctane it produces the opposite chiral, clockwise pore. The prochirality recognition of the solvent molecule in the chiral SAMN pores is attributed to the adaptable conformational changes of the chiral chains of the cDBA molecule.

Lithium-Ion battery silicon Anodes: Surface engineering with novel additives for enhanced ion and electron transport

Silicon (Si) stands as a promising candidate for high-capacity anode materials in the next-generation lithium-ion batteries (LIBs) due to extremely high specific capacity. However, silicon application is hindered by its inherently poor electron and ion conductivities, as well as structural instability during the repeated charging/discharging. To address these challenges, a novel functional surface modification agent, diethylenetriaminepenta(methylenephosphonic) acid (DTPMP), was decorated on the surface of silicon particles for the first time. The experimental results demonstrate that the DTPMP effectively enhances the cohesion between nano Si particles. This study combines experimental observations with theoretical calculations to analyze the nucleophilic and electrophilic sites of DTPMP and carboxymethyl cellulose (CMC), elucidating the existence state of DTPMP on the nano Si surface. Furthermore, by examining the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO), along with the electrostatic potential (ESP) of DTPMP and solvent molecules in conjunction with Li+, the impact of the phosphate group on the diffusion of Li+ and electrons at the nano Si surface was studied. The electron density difference (EDD) maps for DTPMP and CMC reveal that DTPMP exhibits a more pronounced response in the presence of an electric field, suggesting its enhanced role in facilitating Li+ diffusion. This research offers a novel perspective on enhancing the electrochemical performance of nano Si surfaces, paving the way for the development of advanced LIBs with improved energy storage capabilities.

Probing the Effects of Size and Charge on the Monohydration and Dihydration of SiF5- and SiF62- via Comparisons with BF4- and PF6.

This study systematically examines the interactions of the trigonal bipyramidal silicon pentafluoride and octahedral silicon hexafluoride anions with either one or two water molecules, (SiF5-(H2O)n and SiF62-(H2O)n, respectively, where n = 1, 2). Full geometry optimizations and subsequent harmonic vibrational frequency computations are performed using the CCSD(T) ab initio method with a triple-ζ correlation consistent basis set augmented with diffuse functions on all non-hydrogen atoms (cc-pVTZ for H and aug-cc-pVTZ for Si, O, and F; denoted as haTZ). Two monohydrate and six dihydrate minima have been identified for the SiF5-(H2O)n systems, whereas one monohydrate and five dihydrate minima have been identified for the SiF62-(H2O)n systems. Both monohydrated anions have a minimum in which the water molecule adopts a symmetric double ionic hydrogen bond (DIHB) motif with C2v symmetry. However, a second unique monohydrate minimum has been identified for SiF5- in which the water molecule adopts an asymmetric DIHB motif along the edge of the trigonal bipyramidal anion between one axial and one equatorial F atom. This Cs structure is more than 2 kcal mol-1 lower in energy than the C2v local minimum at the CCSD(T)/haTZ level of theory. While the interactions between the solvent and ionic solute are quite strong for the monohydrated anions (electronic dissociation energies of ≈12 and ≈24 kcal mol-1 for the SiF5-(H2O)1 and SiF62-(H2O)1 global minima, respectively), these values are nearly perfectly doubled for the dihydrates, with the lowest-energy SiF5-(H2O)2 and SiF62-(H2O)2 minima exhibiting dissociation energies of ≈24 and ≈47 kcal mol-1, respectively. Structures that form hydrogen bonds between the solvating water molecules also exhibit the largest shifts in the harmonic OH stretching frequencies for the waters of hydration. These shifts can exceed -100 cm-1 for the SiF5-(H2O)2 minimum and -300 cm-1 for the SiF62-(H2O)2 minimum relative to an isolated H2O molecule at the CCSD(T)/haTZ level of theory. This work also corrects the OH stretching frequency shifts for two dihydrate minima of PF6- that were previously erroneously reported ( J. Phys. Chem. A 2020, 124, 8744-8752, DOI: 10.1021/acs.jpca.0c06466).

Gold Nanoclusters whose Photoluminescent Properties are Dynamically Tunable by Modulating the Assembly Pathway Complexity.

Modulating the assembly pathway is an indispensable strategy for optimizing the performance of optical materials. However, implementing this strategy is nontrivial for metal nanocluster building blocks, due to the limited functional modification of nanoclusters and complexity of their emission mechanism. In this report, we demonstrate that a gold nanocluster modified by 4,6-diamino-2-pyrimidinethiol (DPT-AuNCs) self-assembles into two distinct aggregation structures in methanol (MeOH)/water mixed solvent, thus exhibiting pathway complexity. Kinetic studies show that DPT-AuNCs firstly assembles into non-luminescent nanofibers (kinetically controlled), which further transforms into strongly luminescent microflowers (thermodynamicallycontrolled). In-depth analysis of the assembly mechanism reveals that the transformation of aggregation structures involves the disassembly of nanofibers and a subsequent nucleation-growth process. Temperature-dependent photoluminescence (PL) spectroscopy and infrared (IR) measurements reveal that inter-cluster hydrogen bonding bridged by solvent molecules and C-H···π interaction are the key factors for emission enhancement. The photoluminescent property of DPT-AuNCs can be controlled by varying the cosolvent in water, enabling DPT-AuNCs to distinguish different kind of alcohols, particularly the isomerism n-propanol (NPA) and isopropanol (IPA). Additionally, he addition of seeds effectively regulate the assembly kinetics of DPT-AuNCs. This study advances our understanding of assembly pathways and improves the luminescent performance of nanoclusters (NCs).

Dataset for quantum-mechanical exploration of conformers and solvent effects in large drug-like molecules

We here introduce the Aquamarine (AQM) dataset, an extensive quantum-mechanical (QM) dataset that contains the structural and electronic information of 59,783 low-and high-energy conformers of 1,653 molecules with a total number of atoms ranging from 2 to 92 (mean: 50.9), and containing up to 54 (mean: 28.2) non-hydrogen atoms. To gain insights into the solvent effects as well as collective dispersion interactions for drug-like molecules, we have performed QM calculations supplemented with a treatment of many-body dispersion (MBD) interactions of structures and properties in the gas phase and implicit water. Thus, AQM contains over 40 global and local physicochemical properties (including ground-state and response properties) per conformer computed at the tightly converged PBE0+MBD level of theory for gas-phase molecules, whereas PBE0+MBD with the modified Poisson-Boltzmann (MPB) model of water was used for solvated molecules. By addressing both molecule-solvent and dispersion interactions, AQM dataset can serve as a challenging benchmark for state-of-the-art machine learning methods for property modeling and de novo generation of large (solvated) molecules with pharmaceutical and biological relevance.