Dihydrogen Bond Research Articles

Photoelectron Spectroscopy and Computational Study on Microsolvated [B10H10]2- Clusters and Comparisons to Their [B12H12]2- Analogues.

Microhydrated closo-boranes have attracted great interest due to their superchaotropic activity related to the well-known Hofmeister effect and important applications in biomedical and battery fields. In this work, we report a combined negative ion photoelectron spectroscopy and quantum chemical investigation on hydrated closo-decaborate clusters [B10H10]2-·nH2O (n = 1-7) with a direct comparison to their analogues [B12H12]2-·nH2O and free water clusters. A single H2O molecule is found to be sufficient to stabilize the intrinsically unstable [B10H10]2- dianion. The first two water molecules strongly interact with the solute forming B-H···H-O dihydrogen bonds while additional water molecules show substantially reduced binding energies. Unlike [B12H12]2-·nH2O possessing a highly structured water network with the attached H2O molecules arranged in a unified pattern by maximizing B-H···H-O dihydrogen bonding, distinct structural arrangements of the water clusters within [B10H10]2-·nH2O are achieved with the water cluster networks from trimer to heptamer resembling free water clusters. Such a distinct difference arises from the variations in size, symmetry, and charge distributions between these two dianions. The present finding again confirms the structural diversity of hydrogen-bonding networks in microhydrated closo-boranes and enriches our understanding of aqueous borate chemistry.

Hydrogen Bonding vs Dihydrogen Bonding in the Air Stable Primary Phosphine ortho‐Phosphinophenol

Hydrogen Bonding vs Dihydrogen Bonding in the Air Stable Primary Phosphine ortho‐Phosphinophenol

Effect of boron halogenation on dihydrogen bonds: A quantum mechanical approach

Effect of boron halogenation on dihydrogen bonds: A quantum mechanical approach

Potassium Decahydrido-closo-Decaborane Urea Complex as a Potential Solid-State Electrolyte for Potassium Metal Batteries.

All-solid-state potassium metal batteries have been considered promising candidates for large-scale energy storage because of abundance and wide availability of K resources, elimination of flammable liquid organic electrolytes, and incorporation of high-capacity K metal anode. However, unideal K-ion conductivities of most reported K-ion solid electrolytes have restricted the development of these batteries. Herein, a novel K2B10H10·CO(NH2)2 complex is reported, forming by incorporating urea into K2B10H10, to achieve an enhanced K-ion conductivity. The crystal structure of K2B10H10·CO(NH2)2 was determined as a monoclinic lattice with the space group of C2/c (No. 15). K2B10H10·CO(NH2)2 delivers an ionic conductivity of 2.7 × 10-8 S cm-1 at 25 °C, and reaching 1.3 × 10-4 S cm-1 at 80 °C, which is about 4 orders of magnitude higher than that of K2B10H10. One possible reason is the anion expansion in size due to the presence of dihydrogen bonds in K2B10H10·CO(NH2)2, resulting in an increase in the K-H bond distance and the electrostatic potential, thereby enhancing the mobility of K+. The K-ion conductivity is also higher than those of most hydridoborate-based K-ion conductors reported. Besides, K2B10H10·CO(NH2)2 reveals a wide electrochemical stability window and remarkable interface compatibility with K metal electrodes, suggesting a promising electrolyte for all-solid-state K metal batteries.

Cover Feature: Theoretical Insights into Bifurcated Intramolecular Dihydrogen Bonds (ChemPhysChem 4/2024)

Cover Feature: Theoretical Insights into Bifurcated Intramolecular Dihydrogen Bonds (ChemPhysChem 4/2024)

Observation of a super-tetrahedral cluster of acetonitrile-solvated dodecaborate dianion via dihydrogen bonding

We launched a combined negative ion photoelectron spectroscopy and multiscale theoretical investigation on the geometric and electronic structures of a series of acetonitrile-solvated dodecaborate clusters, i.e., B12H122−·nCH3CN (n = 1–4). The electron binding energies of B12H122−·nCH3CN are observed to increase with cluster size, suggesting their enhanced electronic stability. B3LYP-D3(BJ)/ma-def2-TZVP geometry optimizations indicate each acetonitrile molecule binds to B12H122− via a threefold dihydrogen bond (DHB) B3–H3 ⁝⁝⁝ H3C–CN unit, in which three adjacent nucleophilic H atoms in B12H122− interact with the three methyl hydrogens of acetonitrile. The structural evolution from n = 1 to 4 can be rationalized by the surface charge redistributions through the restrained electrostatic potential analysis. Notably, a super-tetrahedral cluster of B12H122− solvated by four acetonitrile molecules with 12 DHBs is observed. The post-Hartree–Fock domain-based local pair natural orbital- coupled cluster singles, doubles, and perturbative triples [DLPNO-CCSD(T)] calculated vertical detachment energies agree well with the experimental measurements, confirming the identified isomers as the most stable ones. Furthermore, the nature and strength of the intermolecular interactions between B12H122− and CH3CN are revealed by the quantum theory of atoms-in-molecules and the energy decomposition analysis. Ab initio molecular dynamics simulations are conducted at various temperatures to reveal the great kinetic and thermodynamic stabilities of the selected B12H122−·CH3CN cluster. The binding motif in B12H122−·CH3CN is largely retained for the whole halogenated series B12X122−·CH3CN (X = F–I). This study provides a molecular-level understanding of structural evolution for acetonitrile-solvated dodecaborate clusters and a fresh view by examining acetonitrile as a real hydrogen bond (HB) donor to form strong HB interactions.

Phase Diagram Analysis of High-Pressure/High-Temperature Polymorphs of Ammonia Borane.

Ammonia borane (NH3BH3) is a promising hydrogen-storage material because of its high hydrogen density. It is employed as a hydrogen source when synthesizing superconducting polyhydrides under high pressure. Additionally, NH3BH3 is a crystallographically interesting compound that features protonic hydrogen (Hδ+) and hydridic hydrogen (Hδ-), and it forms a dihydrogen bond, which explains its stable existence as a solid. Herein, X-ray diffraction experiments were performed at high pressures (HPs) and high temperatures (HTs) of up to 30 GPa and 300 °C, respectively, to investigate the HP/HT phase diagram of NH3BH3. A new HP/HT phase (HPHT2) was identified above 9 GPa and 150 °C. Crystal-structure analysis using the Rietveld method and stability verification using density functional theory calculations revealed that HPHT2 has a P21/n (Z = 4) structure, similar to that of a previously reported HP/HT phase (HPHT) that appears at a lower pressure. HPHT2 is denser than the HP phases that appear at room temperature (HP1 and HP2) at the same pressure (up to ∼17 GPa). In the phase diagram, the phase-boundary line between HPHT and HP1 is a downward convex curve. These unconventional phenomena in the density and phase boundary can be attributed to the influence of dihydrogen bonding on the crystal structure and phase diagram.

Theoretical Insights into Bifurcated Intramolecular Dihydrogen Bonds.

Two-ring intramolecular π-electron delocalization assisted dihydrogen bonds existing in (1Z,4Z)-1,4-dipentene-3-bora-1,5-diol and its symmetrically substituted derivatives have been analysed here since the MP2/6-311++G(d,p) calculations on these systems were performed. The influence of the coexistence of two intramolecular dihydrogen bonded rings in these molecular structures on properties of intramolecular dihydrogen bonds as well as on the π-electron delocalization within these rings was investigated. The comparison with corresponding structures of typical two-ring, so-called resonance-assisted, RAHB, systems was performed. The results of calculations show that such rings' coexistence leads to the weakening of dihydrogen bonds, similarly as for the typical two-ring RAHB systems. The Quantum Theory of ''Atoms in Molecules'' (QTAIM) was also applied here to get more details about the nature of dihydrogen bonds. Correlations between dihydrogen bond strength measures and other energetic, geometrical and topological parameters were also analysed. It was found that characteristics of bond critical points as well as of ring critical points are useful to estimate the strength of intramolecular dihydrogen bonds in two-ring dihydrogen bonded systems discussed here. The Natural Bond Orbital, NBO, approach parameters are also discussed as useful ones to describe properties of dihydrogen bonded systems.

A novel hydrophobic carborane-hybrid microporous material for reversed C2H6 adsorption and efficient C2H4/C2H6 separation under humid conditions.

Since ethylene (C2H4) is important feedstock in the chemical industry, developing economical and energy-efficient adsorption separation techniques based on ethane (C2H6)-selective adsorbents to replace the energy-intensive cryogenic distillation is highly demanded, which however remains a daunting challenge. While previous anionic boron cluster hybrid microporous materials display C2H4-selective features, we herein reported that the incorporation of a neutral para-carborane backbone and aliphatic 1,4-diazabicyclo[2.2.2]octane (DABCO) enables the reversed adsorption of C2H6 over C2H4. The generated carborane-hybrid microporous material ZNU-10 (ZNU = Zhejiang Normal University) is highly stable in humid air and maintains good C2H6/C2H4 separation performance under high humidity. Gas loaded single crystal structure and density-functional theory (DFT) calculations revealed that the weakly polarized carborane and DABCO within ZNU-10 induce more specific C-Hδ+⋯Hδ--B dihydrogen bonds and other van der Waals interactions with C2H6, while the suitable pore space allows the high C2H6 uptake. Approximately 14.5 L kg-1 of polymer grade C2H4 can be produced from simulated C2H6/C2H4 (v/v 10/90) mixtures under ambient conditions in a single step, comparable to those of many popular materials.

IR spectrum of SiH3OH2+SiH4: cationic OH⋯HSi dihydrogen bond versus charge-inverted SiH⋯Si hydrogen bond.

The low electronegativity of Si gives rise to a variety of nonconventional intermolecular interactions in clusters of silanes and their derivatives, which have not been well characterized yet. Herein, we characterize the structures of various isomers of bare and Ar-tagged SiH3OH2+SiH4 dimers composed of protonated silanol and silane by infrared photodissociation (IRPD) of mass-selected ions and dispersion-corrected density functional calculations (B3LYP-D3/aug-cc-pVTZ). The analysis of the IRPD spectra recorded in the OH stretch range reveals the competition between two types of nonconventional hydrogen bonds (H-bonds). The first one represents a OH⋯HSi ionic dihydrogen bond (DHB), in which SiH4 interacts with the H2O moiety of SiH3OH2+. The second one represents a charge-inverted SiH⋯Si ionic H-bond (CIHB), in which the SiH4 ligand interacts with the SiH3 moiety of SiH3OH2+. The latter may also be considered as a weak three-centre two-electron (3c-2e) bond. Although both types of H-bonds are computed to have comparable interaction strengths for SiH3OH2+SiH4 (D0 ≈ 35-40 kJ mol-1), DHB isomers dominate the population in the supersonic plasma expansion, while the abundance of CIHB isomers is roughly one order of magnitude lower, probably as a result of entropic factors.

Responsive structural adaptability in ultra-microporous frameworks: guest recognition and macroscopic shape transformations induced by spin transitions within single crystals

A coordination framework undergoes responsive structural adaptability, associated with spin-crossover activation and CO2/C2H2 separation. Dihydrogen bonds ensure efficient unit functions, enabling a macroscopic shape change in the single crystal.

Carborane-Containing Polymers: Synthesis, Properties, and Applications.

Carboranes are an important class of electron-delocalized icosahedral carbon-boron clusters with unique physical and chemical properties, which can offer various functions to polymers including enhanced heat-resistance, tuned electronic properties and hydrophobicity, special ability of dihydrogen bond formation, and thermal neutron capture. Carborane-containing polymers have been synthesized mainly by means of step-growth polymerizations of disubstituted carborane monomers, with chain-growth polymerizations of monosubstituted carborane monomers including ATRP, RAFT, and ROMP only utilized recently. Carborane-containing polymers may find application as harsh-environment resistant materials, ceramic precursors, fluorescent materials with tuned emissive properties, novel optoelectronic devices, potential BNCT agents, and drug carriers with low cytotoxicity. This review highlights carborane-containing polymer synthesis strategies and potential applications, showcasing the versatile properties and possibilities that this unique family of boron compounds can provide to the polymeric systems.

Investigation of Dihydrogen Bonded Interaction in X3CH⋅⋅⋅HNa, X2CH2⋅⋅⋅HNa (X = F, Cl, and Br) Binary and Ternary Complexes: A DFT and DFT-D3 Approach

Investigation of Dihydrogen Bonded Interaction in X3CH⋅⋅⋅HNa, X2CH2⋅⋅⋅HNa (X = F, Cl, and Br) Binary and Ternary Complexes: A DFT and DFT-D3 Approach

Synthesis and Characterization of (R)‐N‐1‐Cyclohexylethylamine Borane

AbstractA new solid amine borane is reported here. The reaction of (R)‐(−)‐1‐cyclohexylethylamine (a liquid at room temperature) with borane dimethylsulfide yields crystals of pure (R)‐N‐1‐cyclohexylethylamine borane C6H11CH(CH3)NH2BH3 (CHEAB). The successful synthesis was confirmed by molecular analyses (FTIR, Raman and NMR). The crystals are in the form of millimeter‐sized translucent sticks, which allowed determining that CHEAB crystallizes in the orthorhombic system, the space group being P212121. All of the characterization results, together with DFT calculations, strongly suggest the occurrence of intermolecular dihydrogen bonds between antiparallel NH2BH3 groups that are in a trimeric configuration.

Isobaric vapour-liquid equilibrium for systems of propionic acid, butanoic acid and 1,4-butyrolactone at 15.0 kPa

Isobaric vapour-liquid equilibrium (VLE) data for binary systems containing propionic acid (PA) + 1,4-butyrolactone (GBL), butyric acid (BA) + GBL, and PA + BA at 15.0 kPa were measured by using a modified Othmer still. VLE data show that these binary systems are all positive deviation solutions unlike the ideal system. The Herington area test was conducted to confirm the thermodynamic consistency of these binary systems, and positive results were obtained. The interaction energy (Einter) between these components was calculated by molecular simulation to explain the VLE behaviors. Simulation results showed that strongly interacting dihydrogen bonds can form between these acids, which indicated that stable dimer should be present in the vapour phase. In addition, the associating behavior in vapour was corrected using chemical theory, and the activity coefficients of liquid were correlated by the Wilson, the NRTL, and the UNIQUAC models. The correlated results agree well with the experimental values.

Cooperation of Peripheral Hydrogen Atoms for the Stabilization of Aachno-pentaborane (11) with Small Molecules: Hydrogen Bonds and Dihydrogen Bonds

Post-Hartree-Fock calculations performed at the MP2/aug-cc-pVDZ level of theory has been used to analyze the formation of intermolecular complexes between B5H11 and W = CO, NCH, NH3, H2O or HOCH3. The interactions on the structure of the arachno-pentaborane(11) are manifested by the terminal and bridge hydrogen atoms, whereby are formed the hydrogen bonds (H∙∙∙Y with Y = O, C or N) as well as dihydrogen bonds (H∙∙∙H). In this context, the B5H11 shows a host-guest capability for trapping molecules, of course depending on the strength of each aforementioned interactions. The topological descriptors of the Quantum Theory of Atoms in Molecules (QTAIM) were decisive for unveiling each one of the following structures B5H11∙∙∙CO, B5H11∙∙∙NCH, B5H11∙∙∙NH3, B5H11∙∙∙H2O and B5H11∙∙∙HOCH3, and ideally, all hydrogen bonding formed by them.

Exploiting Blood Transport Proteins as Carborane Supramolecular Vehicles for Boron Neutron Capture Therapy.

Carboranes are promising agents for applications in boron neutron capture therapy (BNCT), but their hydrophobicity prevents their use in physiological environments. Here, by using reverse docking and molecular dynamics (MD) simulations, we identified blood transport proteins as candidate carriers of carboranes. Hemoglobin showed a higher binding affinity for carboranes than transthyretin and human serum albumin (HSA), which are well-known carborane-binding proteins. Myoglobin, ceruloplasmin, sex hormone-binding protein, lactoferrin, plasma retinol-binding protein, thyroxine-binding globulin, corticosteroid-binding globulin and afamin have a binding affinity comparable to transthyretin/HSA. The carborane@protein complexes are stable in water and characterized by favorable binding energy. The driving force in the carborane binding is represented by the formation of hydrophobic interactions with aliphatic amino acids and BH-π and CH-π interactions with aromatic amino acids. Dihydrogen bonds, classical hydrogen bonds and surfactant-like interactions also assist the binding. These results (i) identify the plasma proteins responsible for binding carborane upon their intravenous administration, and (ii) suggest an innovative formulation for carboranes based on the formation of a carborane@protein complex prior to the administration.

Towards the Application of Purely Inorganic Icosahedral Boron Clusters in Emerging Nanomedicine.

Traditionally, drugs were obtained by extraction from medicinal plants, but more recently also by organic synthesis. Today, medicinal chemistry continues to focus on organic compounds and the majority of commercially available drugs are organic molecules, which can incorporate nitrogen, oxygen, and halogens, as well as carbon and hydrogen. Aromatic organic compounds that play important roles in biochemistry find numerous applications ranging from drug delivery to nanotechnology or biomarkers. We achieved a major accomplishment by demonstrating experimentally/theoretically that boranes, carboranes, as well as metallabis(dicarbollides), exhibit global 3D aromaticity. Based on the stability-aromaticity relationship, as well as on the progress made in the synthesis of derivatized clusters, we have opened up new applications of boron icosahedral clusters as key components in the field of novel healthcare materials. In this brief review, we present the results obtained at the Laboratory of Inorganic Materials and Catalysis (LMI) of the Institut de Ciència de Materials de Barcelona (ICMAB-CSIC) with icosahedral boron clusters. These 3D geometric shape clusters, the semi-metallic nature of boron and the presence of exo-cluster hydrogen atoms that can interact with biomolecules through non-covalent hydrogen and dihydrogen bonds, play a key role in endowing these compounds with unique properties in largely unexplored (bio)materials.

Synergistic effects of caesium closo-dodecaborate on buried interface for efficient and stable perovskite solar cells

The defects and strain of the buried SnO2/perovskite interface seriously affects the performances of n-i-p type perovskite solar cells. Herein, caesium closo-dodecaborate (B12H12Cs2) is introduced into buried interface to improve the device performances. B12H12Cs2 can passivate the bilateral defects of the buried interface, including the oxygen vacancy and uncoordinated Sn2+ defects on SnO2 side and the uncoordinated Pb2+ defects on perovskite side. Three-dimensional aromatic B12H12Cs2 can promote the interface charge transfer and extraction. [B12H12]2− can enhance the interface connection of buried interface by forming B-H---H-N dihydrogen bond and coordination bonds with metal ions. Meanwhile, the crystal properties of perovskite films can be improved and the buried tensile strain can be released by B12H12Cs2 due to the matched lattice between B12H12Cs2 and perovskite. In addition, Cs+ can diffuse into perovskite to reduce the hysteresis behavior by inhibiting the I− migration. Arising from the enhanced connection performances, passivated defects, improved perovskite crystallization, enhanced charge extraction, inhibited ions migration, released tensile strain at buried interface by B12H12Cs2, the corresponding devices yield a champion power conversion efficiency of 22.10% with enhanced stability. The stability of devices by B12H12Cs2 modification have been improved, and it can still maintain 72.5% of the original efficiency after 1440 h, while the control devices can only maintain 20% of the original efficiency after aging in air condition of 20–30% RH.

Effects of NH4+ doping on the hydrogen storage properties of metal hydrides

Doping can modify the properties of metal hydrogen storage materials significantly. Currently, the metal doping is a frequent strategy, while the non-metal cation doping has not been examined extensively so far. In this study, the effects of NH4+ doping on the hydrogen storage properties of different metal hydrides, including TiH2, Ti0·25V0·25Nb0·25Zr0·25H2, Ti0·5V0·5H2 and VH2, are investigated by first-principles calculations. It is found that the NH4+ presents a good affinity for metal hydrides and the NH4+ incorporation leads to charge redistribution and formation of dihydrogen bond. Furthermore, the NH4+ doping in metal hydrides is favorable for enhancing the hydrogen storage capacity and decreasing the thermal stability simultaneously. The possible reason for the NH4+ doping induced destabilization in metal hydrides is the relatively weak interaction between NH4+ and hydrogen atoms.