Hydrocarbon Ligands Research Articles

Fusing Bismuth and Mercaptocarboranes: Design and Biological Evaluation of Low-Toxicity Antimicrobial Thiolato Complexes.

This study proposes an innovative strategy to enhance the pharmacophore model of antimicrobial bismuth thiolato complex drugs by substituting hydrocarbon ligand structures with boron clusters, particularly icosahedral closo-dicarbadodecaborane (C2B10H12, carboranes). The hetero- and homoleptic mercaptocarborane complexes BiPh2L (1) and BiL3 (2) (L=9-S-1,2-C2B10H11) were prepared from 9-mercaptocarborane (HL) and triphenylbismuth. Comprehensive characterization using NMR, IR, MS, and XRD techniques confirmed their successful synthesis. Evaluation of antimicrobial activity in a liquid broth microdilution assay demonstrated micromolar to submicromolar minimum inhibitory concentrations (MIC) suggesting high effectiveness against S. aureus and limited efficacy against E. coli. This study highlights the potential of boron-containing bismuth complexes as promising antimicrobial agents, especially targeting Gram-positive bacteria, thus contributing to the advancement of novel therapeutic approaches.

Tuning of optical properties and phase behavior of Nanomaterial-stabilized blue phase liquid crystals

HypothesisNanoparticles of various shapes and sizes can affect the optical properties and blue phase (BP) stabilization of BP liquid crystals (BPLCs). This is because nanoparticles, which are more compatible with the LC host, can be dispersed in both the double twist cylinder (DTC) and disclination defects in BPLCs. ExperimentsThis study presents the first systematic study of the use of CdSe nanoparticles having various sizes and shapes (spheres, tetrapods and nanoplatelets) to stabilize BPLCs. Unlike previous studies using commercial nanoparticles (NPs), we custom-synthesized NPs with the same core and nearly identical long chain hydrocarbon ligand materials. Two LC hosts were used to investigate the NP effect on BPLCs. FindingsThe size and shape of nanomaterials greatly influence the interaction with LCs, and the dispersion of NPs in the LC medium affects the position of the BP reflection band and the stabilization of BPs. Spherical NPs were found to be more compatible with the LC medium than tetrapod shape and platelet shape NPs, resulting in a wider temperature range of BP and a redshift of the reflection band of BP. In addition, the inclusion of spherical NPs tuned the optical properties of BPLCs to a significant extent, whereas BPLCs with nanoplatelets displayed a limited influence on the optical properties and temperature window of BPs due to poor compatibility with LC hosts. The tunable optical behavior of BPLC as a function of the type and concentration of NPs has not been reported.

Superbright quantum dots with inorganic caps

Inorganic semiconductor nanocrystals, or quantum dots, are widely used in commercial displays and imaging technology. They could be used in additional optoelectronic applications if their charge-transport properties could be improved without dimming their intense luminescence. A new study reports a way to do that by treating the crystals with metal salts to customize the quantum dots’ surface chemistry ( Nat. Commun. 2023, DOI: 10.1038/s41467-022-35702-7 ). Quantum dots are typically capped with long-chain hydrocarbon ligands to control crystal growth and stabilize the particles in colloidal suspensions. They also form electrically insulating barriers that impede charge flow between particles, a property needed for electronic applications. Replacing the organic ligands with inorganic ones can boost charge transport, but that approach can reduce luminescence by over 75%. Yuanyuan Wang of Nanjing University, Dmitri V. Talapin of the University of Chicago, and coworkers treated organically capped quantum dots with salts of cadmium, zinc, and other

A general confinement co-assembly strategy enabling cross-dimensional supraspheres for boosting electrochemical performance

The bottom-up assembly utilizing nanocrystals (NCs) as building blocks is a highly anticipated approach to access novel metamaterials. Limited by the library of binary spherical assembly, colloidal components of building blocks are necessarily extended for targeting the desired assembled-superstructure with emergent properties. Here, a generalized approach is presented that carbon nanotubes (CNTs) capped with long-chain hydrocarbon ligands, as creative colloidal components, can be compatibly co-assembled with various NCs into binary supraspheres based on a confinement microemulsion environment. Such cross-dimensional assemblies possess the structural merits of excellent conductivity, abundant voids and high stability, thus synergistically boosting its electrochemical performance. As a proof of concept, the co-assembled CoFe 2 O 4 /CNTs supraspheres exhibit extraordinary capacity (890 mAh g −1 at 0.5 A g −1 ), rate capability (318 mAh g −1 at 20 A g −1 ), and structural stability (458 mAh g −1 at 5 A g −1 after 1000 cycles) relative to pure CoFe 2 O 4 when evaluated in Li-ion battery. Beyond that, its derived phosphides CoFeP/CNTs assemblies outperform most of the state-of-art electrodes when acting as electrocatalysts for hydrogen evolution reactions (HER). This work provides a new perspective for constructing superstructures of NCs for potential applications in energy storage devices.

Beyond Steric Crowding: Dispersion Energy Donor Effects in Large Hydrocarbon Ligands.

Interactions between sterically crowded hydrocarbon-substituted ligands are widely considered to be repulsive because of the intrusion of the electron clouds of the ligand atoms into each other's space, which results in Pauli repulsion. Nonetheless, there is another interaction between the ligands which is less widely publicized but is always present. This is the London dispersion (LD) interaction which can occur between atoms or molecules in which dipoles can be induced instantaneously, for example, between the H atoms from the ligand C-H groups.These LD interactions are always attractive, but their effects are not as widely recognized as those of the Pauli repulsion despite their central role in the formation of condensed matter. Their relatively poor recognition is probably due to the relative weakness (ca. 1 kcal mol-1) of individual H···H interactions owing to their especially strong distance dependence. In contrast, where there are numerous H···H interactions, a collective LD energy equaling several tens of kcal mol-1 may ensue. As a result, in some molecules the latent importance of the LD attraction energies emerges and assumes a prominence that can overshadow the Pauli effects (e.g., in the stabilization of high-oxidation-state transition-metal alkyls, inducing disproportionation reactions, or in the stabilization of otherwise unstable bonds).Despite being known for over a century, the accurate quantification of individual H···H LD effects in molecular species is a relatively recent phenomenon and at present is based mainly on modified DFT calculations. A few leading reviews summarized these earlier studies of the C-H···H-C LD interactions in organic molecules, and their effects on the structures and stabilities were described. LD effects in sterically crowded inorganic and organometallic molecules have been recognized.The author's interest in these LD effects arose fortuitously over a decade ago during research on sterically crowded heavier main-group element carbene analogues and two-coordinate, open-shell (d1-d9) transition-metal complexes where counterintuitive steric effects were observed. More detailed explanations of these effects were provided by dispersion-corrected DFT calculations in collaboration with the groups of Tuononen and Nagase (see below).This Account describes our development of these initial results for other inorganic molecular classes. More recently, the work has led us to move to the planned inclusion of dispersion effects in ligands to stabilize new molecular types with theoretical input from the groups of Vasko and Grimme (see below). Our approach sought to use what Grimme has described as dispersion effect donor (DED) groups (i.e., spatially close-lying, densely packed substituents either as ligands (e.g., -C6H2-2,4,6-Cy3, Cy = cyclohexyl) or as parts of ligands (e.g., a Cy substituent) that produce relatively large dispersion energies to stabilize these new compounds.We predict that the future design of sterically crowding hydrocarbon ligands will include the consideration and incorporation of LD effects as a standard methodology for directed use in the attainment of new synthetic targets.

Al-alkyls as acceptor dopant precursors for atomic-scale devices

Atomically precise ultradoping of silicon is possible with atomic resists, area-selective surface chemistry, and a limited set of hydride and halide precursor molecules, in a process known as atomic precision advanced manufacturing (APAM). It is desirable to expand this set of precursors to include dopants with organic functional groups and here we consider aluminium alkyls, to expand the applicability of APAM. We explore the impurity content and selectivity that results from using trimethyl aluminium and triethyl aluminium precursors on Si(001) to ultradope with aluminium through a hydrogen mask. Comparison of the methylated and ethylated precursors helps us understand the impact of hydrocarbon ligand selection on incorporation surface chemistry. Combining scanning tunneling microscopy and density functional theory calculations, we assess the limitations of both classes of precursor and extract general principles relevant to each.

Cover Feature: Heterometallic d8–d10 Coupling of Rh(I) and M(0) (M=Pd, Pt) in a Sandwich Framework of π‐Conjugated Ligands (Chem. Eur. J. 41/2021)

A sandwich framework of π-conjugated unsaturated hydrocarbon ligands was found to provide a unique coordination environment that facilitates unusual coupling of d8 RhI and d10 M0 (M=Pd, Pt). The molecular orbital analysis showed that the electron-accepting ability of the sandwich framework through back-donation allows the formation of a dσ-type Rh-Pd bond in a (d-d)18 electron system. More information can be found in the Communication by S. Sakaki, T. Murahashi, et al. (DOI: 10.1002/chem.202101133).

Heterometallic d8 -d10 Coupling of Rh(I) and M(0) (M=Pd, Pt) in a Sandwich Framework of π-Conjugated Ligands.

A heterometallic M-M' bond formation is a key to construct atomically precise bimetallic clusters and materials. However, it is sometimes not straightforward to construct a heterometallic M-M' bond through conventional methods including redox condensation. Here, we found that a sandwich framework of π-conjugated unsaturated hydrocarbon ligands provides a unique coordination environment that facilitates unusual coupling of d8 RhI and d10 M0 (M=Pd, Pt). The molecular orbital analysis showed that the electron-accepting ability of the sandwich framework through back-donation allows the formation of a dσ-type Rh-Pd bond in a (d-d)18 electron system.

Polycyclic aromatic hydrocarbons in airborne particulate matter samples from Hanoi, Vietnam: Particle size distribution, aryl hydrocarbon ligand receptor activity, and implication for cancer risk assessment

Concentrations and profiles of unsubstituted and methylated polycyclic aromatic hydrocarbons (PAHs and Me-PAHs) were analyzed in airborne particulate matter (PM) samples collected from high-traffic roads in Hanoi urban area. Levels of PAHs and Me-PAHs ranged from 210 to 660 (average 420) ng/m3 in total PM, and these pollutants were mainly associated with fine particles (PM2.5) rather than coarser ones (PM > 10 and PM10). Proportions of high-molecular-weight compounds (i.e., 5- and 6-ring) increased with decreasing particle size. Benzo[b+k]fluoranthene, indeno[1,2,3-cd]pyrene, and benzo[ghi]perylene were the most predominant compounds in the PM2.5 samples. In all the samples, Me-PAHs were less abundant than unsubstituted PAHs. The PAH-CALUX assays were applied to evaluate aryl hydrocarbon receptor (AhR) ligand activities in crude extracts and different fractions from the PM samples. Benzo[a]pyrene equivalents (BaP-EQs) derived by the PAH-CALUX assays for low polar fractions (mainly PAHs and Me-PAHs) ranged from 300 to 840 ng/m3, which were more consistent with theoretical values derived by using PAH-CALUX relative potencies (270–710 ng/m3) rather than conventional toxic equivalency factor-based values (22–69 ng/m3). Concentrations of PAHs and Me-PAHs highly correlated with bioassay-derived BaP-EQs. AhR-mediated activities of more polar compounds and interaction effects between PAH-related compounds were observed. By using PAH-CALUX BaP-EQs, the ILCR values ranged from 1.0 × 10−4 to 2.8 × 10−4 for adults and from 6.4 × 10−5 to 1.8 × 10−4 for children. Underestimation of cancer risk can be eliminated by using effect-directed method (e.g., PAH-CALUX) rather than chemical-specific approach.

Bismuth Atoms in Hydrocarbon Ligands: Bismepines as Rigid, Ditopic Arene Donors in Coordination Chemistry

Dibenzobismepines may be described as bismuth heterocycles containing two arene functional groups (see the graphic). The coordination chemistry of mono- and dinuclear bismepines has been investigat...

Applications of a grid-based CYP3A4 Template system to understand the interacting mechanisms of large-size ligands; part 4 of CYP3A4 Template study

Catalytic interactions of CYP3A4 with large-size ligands have been studied on the Template established in our previous studies using polyaromatic hydrocarbon and steroid ligands (DMPK 34: 113–125 and 351–364 2019 and in press 2020). Typical CYP3A4-substrates including erythromycin, cyclosporin A (ca.1200 Da), ivermectin B1a and taxanes were applied successfully and regioselective metabolisms of these ligands were reconstituted faithfully on Template. These results suggest the applicability of CYP3A4 Template throughout broadened sizes of CYP3A4 ligands. Macrolide antibiotics showed distinct degrees of tight sittings in Width-gauge, a tool for accommodation measure. The observed differences were associated with different inhibitory/inactivation potentials of troleandomycin, erythromycin, clarithromycin and azithromycin, suggesting CYP3A4 Template also as a tool for drug-interaction mechanisms. Slight expansion of Template area was made at near Site of oxidation from simulation results of antitumor agent, rilpivirine, in the present study. Ligand entry from left side of Template is also suggested from macrolide interactions. Broadened applicability of the refined CYP3A4 Template were assured with experiments with various large-size ligands.

Spin Transport Properties of One-Dimensional Benzene Ligand Organobimetallic Sandwich Molecular Wires.

Organometallic sandwich complexes, composed of cyclic hydrocarbon ligands and transition-metal atoms, display unique physical and chemical properties. In this work, the electronic and spin transport properties of one-dimensional (1D) VBz2 ligand bimetallic sandwich complexes, VBz2–TM (TM = Cr, Mn, and Fe), are systematically investigated using density functional theory and nonequilibrium Green’s function method. The results show that all the 1D infinite molecular wires [(VBz2)TM]∞ (TM = Cr–Fe) are found to be thermodynamically stable with high binding energies (∼1.0–3.45 eV). In particular, they are predicted to be ferromagnetic half metals. Moreover, the I–V curves exhibit negative differential resistance for one, two, and three VBz2–TM wires at TM = Cr, Mn, and Fe, respectively, which is of great significance for certain electronic applications. Our findings strongly suggest that the benzene ligand bimetallic sandwich molecular wires are good candidates for potential electronics and spintronics.

Ligand conformations and spin states in sandwich-type complexes of the split (3+2) five-electron donor hydrocarbon ligand bicyclo[3.2.1]octa-2,6-dien-4-yl (bcod)

Sandwich-type structures are energetically preferred for the bis(bicyclo[3.2.1]octa-2,6-dien-4-yl) complexes of the first row transition metals (bcod)2M including the experimentally known chromium and iron derivatives.

Imine Metathesis by Silica-Supported Catalysts Using the Methodology of Surface Organometallic Chemistry.

With this protocol, a well-defined singlesite silica-supported heterogeneous catalyst [(≡Si-O-)Hf(=NMe)(η1-NMe2)] is designed and prepared according to the methodology developed by surface organometallic chemistry (SOMC). In this framework, catalytic cycles can be determined by isolating crucial intermediates. All air-sensitive materials are handled under inert atmosphere (using gloveboxes or a Schlenk line) or high vacuum lines (HVLs, <10-5 mbar). The preparation of SiO2-700 (silica dehydroxylated at 700 °C) and subsequent applications (the grafting of complexes and catalytic runs) requires the use of HVLs and double-Schlenk techniques. Several well-known characterization methods are used, such as Fourier-transform infrared spectroscopy (FTIR), elemental microanalysis, solid-state nuclear magnetic resonance spectroscopy (SSNMR), and state-of-the-art dynamic nuclear polarization surface enhanced NMR spectroscopy (DNP-SENS). FTIR and elemental microanalysis permit scientists to establish the grafting and its stoichiometry. 1H and 13C SSNMR allows the structural determination of the hydrocarbon ligands coordination sphere. DNP SENS is an emerging powerful technique in solid characterization for the detection of poorly sensitive nuclei (15N, in our case). SiO2-700 is treated with about one equivalent of the metal precursor compared to the amount of surface silanol (0.30 mmol·g-1) in pentane at room temperature. Then, volatiles are removed, and the powder samples are dried under dynamic high vacuum to afford the desired materials [(≡Si-O-)Hf(η2π-MeNCH2)(η1-NMe2)(η1-HNMe2)]. After a thermal treatment under high vacuum, the grafted complex is converted into metal imido silica complex [(≡Si-O-)Hf(=NMe)(η1-NMe2)]. [(≡Si-O-)Hf(=NMe)(η1-NMe2)] effectively promotes the metathesis of imines, using the combination of two imine substrates, N-(4-phenylbenzylidene)benzylamine, or N-(4-fluorobenzylidene)-4-fluoroaniline, with N-benzylidenetert-butylamine as substrates. A significantly lower conversion is observed with the blank runs; thus, the presence of the imido group in [(≡Si-O-)Hf(=NMe)(η1-NMe2)] is correlated to the catalytic performance.

Stability, Thermal Conductivity, Viscosity, and Tribological Characterization of Zirconia Nanofluids as a Function of Nanoparticle Concentration

Commercially prepared spherical zirconia (ZrO2) nanoparticles with an average particle diameter of 5 nm and functionalized with a hydrocarbon ligand were dispersed in a polyalphaolefin (PAO) base oil, producing a 10-nm stabilized zirconia nanofluid. The resulting nanofluid’s properties were characterized, including thermal conductivity and viscosity. A preliminary study of the nanofluid’s ability to generate protective tribofilms was conducted. Long-term stability was verified using dynamic light scattering (DLS) and average particle size was quantified as a function of time. A 10 wt% ZrO2 nanofluid maintained a 10-nm average particle size over 25 months, with no signs of agglomeration or sedimentation, and redispersion was not necessary before analysis. The tribological performance of several concentrations of ZrO2 nanofluids wasdisc characterized with a ball-on-disc tribometer. Tribofilm growth over time was collected via optical interference imaging. Friction data collected over time are also reported. Nanoparticle concentration was varied to understand its effect on tribofilm growth. The ZrO2 tribofilm morphology and chemistry were characterized using scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), and transmission electron microscopy (TEM).

Exceeding Metal Capacity in Sandwich Complexes: Ligand-Unsupported Docking of Extra Metal Moieties at Edges of a Metal Sheet Sandwich Complex.

The ligand-unsupported accommodation of extra metal moieties in a sandwich complex is reported. Although it has been considered that the metal-capacity of a metal sheet sandwich complex is strictly limited by the size of cyclic unsaturated hydrocarbon ligands, the M-M edge bonds in a metal sheet sandwich complex provide a ligand-unsupported docking site for extra metal moieties, allowing expansion of metal-capacity in sandwich complexes. The metal sheet sandwich complex [Pd4 (μ4 -C8 H8 )(μ4 -C9 H9 )]+ , in which the ligand-based metal capacity is full in terms of the usage of all C=C moieties of the smaller carbocyclic ligand C8 H8 in coordination, can accommodate extra M0 {P(OPh)3 }2 (M=Pd, Pt) moieties without coordinative assistance by either the C9 H9 or the C8 H8 ligand.

Exceeding Metal Capacity in Sandwich Complexes: Ligand‐Unsupported Docking of Extra Metal Moieties at Edges of a Metal Sheet Sandwich Complex

AbstractThe ligand‐unsupported accommodation of extra metal moieties in a sandwich complex is reported. Although it has been considered that the metal‐capacity of a metal sheet sandwich complex is strictly limited by the size of cyclic unsaturated hydrocarbon ligands, the M−M edge bonds in a metal sheet sandwich complex provide a ligand‐unsupported docking site for extra metal moieties, allowing expansion of metal‐capacity in sandwich complexes. The metal sheet sandwich complex [Pd4(μ4‐C8H8)(μ4‐C9H9)]+, in which the ligand‐based metal capacity is full in terms of the usage of all C=C moieties of the smaller carbocyclic ligand C8H8 in coordination, can accommodate extra M0{P(OPh)3}2 (M=Pd, Pt) moieties without coordinative assistance by either the C9H9 or the C8H8 ligand.

General Mild Reaction Creates Highly Luminescent Organic-Ligand-Lacking Halide Perovskite Nanocrystals for Efficient Light-Emitting Diodes.

The presence of labile bulky insulating hydrocarbon ligands in halide perovskite nanocrystals (NCs) passivates surface traps but concurrently makes charge transport difficult in optoelectronic devices. Early efforts routinely rely on the replacement of long-chain ligands with short-chain cousins, leading to notable changes in NC's sizes and photophysical properties and thus making it hard to obtain devices with nearly designed emissions. Here we report a general solution-phase ligand-exchange strategy to produce organic-ligand-lacking halide perovskite NCs with high photoluminescence (PL) quantum yields and good stability in ambient air. We demonstrate that the ligand exchange can be achieved by a well-controlled mild reaction of thionyl halide with the carboxylic and amine groups on the NC's surface, resulting in nearly dry NCs with well-passivated surfaces and almost unaltered emission characteristics. Consequently, we achieve exceptionally high-performance blue perovskite NC light-emitting diodes (LEDs) with an external quantum efficiency of up to 1.35% and an extremely narrow full width at half-maximum of 14.6 nm. Our work provides a systematic framework for preparing high-quality organic-ligand-lacking perovskite NC inks that can be directly cast as films featuring effective charge transport, thereby providing the foundation for further development of a wide range of efficient perovskite optoelectronic devices.

Isolation and Identification of Aryl Hydrocarbon Receptor Modulators in White Button Mushrooms (Agaricus bisporus).

Natural aryl hydrocarbon (AHR) ligands have been identified in food and herbal medicines, and they may exhibit beneficial activity in humans. In this study, white button (WB) feeding significantly decreased AHR target gene expression in the small intestine of both conventional and germ-free mice. High-performance liquid chromatography (HPLC) fractionation and ultra-high-performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) combined with an AHR-responsive cell-based luciferase gene reporter assay were used to isolate and characterize benzothiazole (BT) derivatives and 6-methylisoquinoline (6-MIQ) as AHR modulators from WB mushrooms. The study showed dose-dependent changes of AHR transformation determined by the cell-based luciferase gene reporter assay and transcription of CYP1A1 in human Caco-2 cells by BT derivatives and 6-MIQ. These findings suggested that WB mushroom contains new classes of natural AHR modulators and demonstrated HPLC fractionation and UHPLC-MS/MS combined with a cell-based luciferase gene reporter assay as a useful approach for isolation and characterization of the previously unidentifed AHR modulators from natural products.

Designing Strong Optical Absorbers via Continuous Tuning of Interparticle Interaction in Colloidal Gold Nanocrystal Assemblies.

We program the optical properties of colloidal Au nanocrystal (NC) assemblies via an unconventional ligand hybridization (LH) strategy to precisely engineer interparticle interactions and design materials with optical properties difficult or impossible to achieve in bulk form. Long-chain hydrocarbon ligands used in NC synthesis are partially exchanged, from 0% to 100%, with compact thiocyanate ligands by controlling the reaction time for exchange. The resulting NC assemblies show transmittance, reflectance, optical permittivity, and direct-current (DC) resistivity that continuously traverse a dielectric-metal transition, providing analog tuning of their physical properties, unlike the digital control realized by complete exchange with ligands of varying length. Exploiting this LH strategy, we create Au NC assemblies that are strong, ultrathin film optical absorbers, as seen by a 6× increase in the extinction of infrared light compared to that in bulk Au thin films and by a temperature rise of 20 °C upon illumination with 808 nm light. Our LH strategy may be applied to the design of materials constructed from NCs of different size, shape, and composition for specific applications.