Synergic effect of hydrogen bonding and dipole repulsion in the ring-closing metathesis of N-homoallyl-2-(hydroxymethyl)acrylamides

This study reveals that the Ru-catalyzed ring-closing metathesis of N-homoallyl-2-(hydroxymethyl)acrylamides is promoted by substrate-catalyst hydrogen bonding as well as dipole repulsion between the electron-rich side-chain and the carbonyl group, providing clues for designing effective synthetic routes towards 5,6-dihydro-2(1H)-pyridinones.     

Electrochemical measurement of switchable hydrogen bonding in an anthraquinone-based anion receptor

The electrochemistry of a novel anion receptor is presented. The receptor 1,3-diphenylcarboxamidoanthraquinone (AAR) in the absence of an appropriate anion behaves as an anthraquinone system in the presence of a strong hydrogen bond donor. In this case, the electrochemical evidence supports the suggestion that the hydrogen bonding with the anthraquinone occurs at least partially through intra- or intermolecular interactions. It is suggested that these interactions stabilise both the semiquinone and dianion species resulting from reduction of AAR. However, in the presence of a suitable competitive anion (specifically F⁻), the hydrogen-bond donor groups bind to the anion rather than the quinone oxygen atoms. This removes the hydrogen bonding interaction to the redox-active quinone centre and hence alters the electrochemistry significantly. In the presence of F⁻, two one-electron quasireversible electrochemical processes are observed.     

Modeling chemical reactions on surfaces: The roles of chemical bonding and van der Waals interactions

Chemical reactions on surfaces play central roles in heterogeneous catalysis, and most reactions involve the formation and/or the cleavage of bonds. At present, density functional theory (DFT) has become the workhorse for computational investigation of reaction mechanisms, but its predictive power has been severely limited by the lack of appropriate exchange-correlation functionals. Here, we show that there are many cases where the chemical bonding and van der Waals (vdW) interactions both play a key role in chemical reactions on surfaces. After briefly introducing some DFT methods and basic theory in chemical reactions, we first demonstrate that DFT can help to understand the mechanisms of “classic” reactions that mainly dominated by covalent bonding and vdW forces, as exemplified in electrocatalytic reduction of CO₂ and the fabrication of 2D materials on metal substrates. We next show that DFT calculations can help to uncover the tautomerization reactions of molecules on metal surfaces, wherein the hydrogen bonding and vdW forces would largely affect the reaction process. More importantly, we show that in some cases, the vdW interactions can become the decisive effect that determines the adsorption configuration, energy hierarchy, and the potential-energy surface of chemical reactions, yielding distinct pathways and products. Additionally, we highlight the importance of more realistic conditions, such as surface defects, finite coverage, and temperature effects, in accurate modeling of chemical reactions. Finally, we summarize some challenges in modeling catalysis, which include many-body dispersive correction, strong correlation effect, and non-adiabatic approximations.     

Substituent effects on the isomerization of hydrazone switches driven by the intramolecular hydrogen bond

In this work, the substituent effects on hydrogen bonding in one kind of hydrazone-based switch are revealed. The E/Z isomerization ratios of these hydrazones and their intramolecular hydrogen bond strengths in the Z form were evaluated using NMR technique. Linear correlations between these parameters and Hammett empirical values for substituent effects are explored as well.     

1,2,3-三氮杂苯-水簇复合物氢键结构与性质的理论研究

在B3LYP/6-31 G**水平上对1,2,3-三氮杂苯和水形成1∶1,1∶2和1∶3复合物的基态氢键结构进行几何优化和性质计算,结果表明复合物之间存在较强的氢键作用。氢键的形成使水分子中H-O键振动频率减小(红移)。NBO分析表明,最稳定的1∶1,1∶2和1∶3复合物发生分子间电荷转移总量分别为0.0222e,0.0261e和0.0273e。     

Naked-eye detection of F and AcO ions by Schiff base receptor

A Schiff base 2, composed with o-phenylenediamine and 5-nitro-salicylaldehyde have been synthesized as an anion receptor. It consists with conjugated imine, phenolic -OH and electron withdrawing substituent nitro (-NO₂) group. Receptor 2 can recognize selectively biologically important F⁻ and AcO⁻ ions. The recognition properties have been investigated by naked-eye color change (colorless to yellow), followed by UV-vis spectral changes. Predicted stoichiometries of the complexes between receptor 2 and anions based on density functional theory (DFT) level calculations, corroborates well with experimental findings.     

Hydrogen and dihydrogen bonding of transition metal hydrides

Intermolecular interactions between a prototypical transition metal hydride WH(CO)₂NO(PH₃)₂ and a small proton donor H₂O have been studied using DFT methodology. The hydride, nitrosyl and carbonyl ligand have been considered as site of protonation. Further, DFT-D calculations in which empirical corrections for the dispersion energy are included, have been carried out. A variety of pure and hybrid density functionals (BP86, PW91, PBE, BLYP, OLYP, B3LYP, B1PW91, PBE0, X3LYP) have been considered, and our calculations indicate the PBE functional and its hybrid variation are well suited for the calculation of transition metal hydride hydrogen and dihydrogen bonding. Dispersive interactions make up for a sizeable portion of the intermolecular interaction, and amount to 20–30% of the bond energy and to 30–40% of the bond enthalpy. An energy decomposition analysis reveals that the H?H bond of transition metal hydrides contains both covalent and electrostatic contributions.     

Methyl hydrogen peroxide dimer: A structural study

Methyl hydrogen peroxide (MHP) exhibits a tendency to form a stable dimer by hydrogen-bonding. Ab initio theoretical investigations on methyl hydrogen peroxide dimer (MHPD) carried out herein lead to several energetically stable structures that have a direct bearing on the reactivity of the monomer in terms of its molecular electrostatic potential (MESP). To gauge the role played by the electron-correlation in lending stability to MHP and its dimer, we employ the density functional theory (DFT) (as implemented by B3LYP-functional), and subsequently second order Møller-Plesset (MP2) perturbation theory, using the basis sets 6-31G(d, p) and 6-311++G(2d, 2p). Simulated infra-red vibrational spectra lead to spectral intensity redistribution upon dimerization. Energetically the lowest MHPD is endowed with inversion symmetry and has two hydrogen bonds, while three other structures emerge: one energetically very close with two H-bonds, and the two others, with three H-bonds each, yet higher by about 2 kcal mol⁻¹.     

Modulation of hydrogen bonding upon ion binding: Insights into cooperativity

The impact due to the of presence of ions, such as Mg²⁺, Na⁺, H⁺, Cl^?, and OH^? on hydrogen bonded clusters of increasing size (water, formamide, and acetamide [n = 1–10]) in the context of associated cooperativity has been explored using density functinal theory (DFT) calculations. Sequential binding energies (SBE) rise on addition of monomer in case of parent clusters. SBE for ionic clusters are several times higher than that of parent clusters initially. This behavior is more dramatic on addition of either Mg²⁺ or H⁺ compared to other ions. Interestingly, SBE of both parent and ionic clusters approach nearly uniform values beyond n = 6 irrespective of kind of ion present in the cluster with the exception of magnesium. © 2013 Wiley Periodicals, Inc.     

First-principles study of hydrogen adsorption on Mo(1 1 0)

First-principles calculations based on density functional theory-generalized gradient approximation method have been performed for hydrogen (H) adsorption on Mo(1 1 0) surface. For various coverages, the hollow (hol) site was found to be the most stable binding site. The adsorption energy of this site was slightly increased as the increasing of hydrogen coverage. Subsurface (sub) occupation at low and medium coverages was ruled out while it became to be stable at the coverage of 1 ML. This is also supported by the potential energy surface (PES) study for hydrogen diffusing from hol to sub site. It’s interesting to find a surface reconstruction at the coverage of 1 ML, which is characterized by the lateral shift of the topmost layer for the sub adsorption. At higher coverage, the local density of states (LDOS) analysis showed that a new peak was clearly visible which was ascribed to a surface state induced by hydrogen adsorption. This surface state was mostly localized on the hydrogen atom and the first Mo layer, implying the hybridization of the hydrogen 1s states and the Mo metal states.     

Stereoselective synthesis of alicyclic ketones: A hydrogen borrowing approach

A highly diastereoselective annulation strategy for the synthesis of alicyclic ketones from diols and pentamethylacetophenone is described. This process is mediated by a commercially available iridium(III) catalyst, and provides efficient access to a wide range of cyclopentane and cyclohexane products with high levels of stereoselectivity. The origins of diastereoselectivity in the annulation reaction have been explored by a series of control experiments, which provides an explanation for how each stereocentre around the newly forged ring is controlled.     

Density functional theory study of the hydrogen bonding interaction of 1:1 complexes of serine with water

The hydrogen bonding of 1:1 complexes formed between serine and water molecules were completely investigated in the present study employing ab initio and Density Functional Theory (DFT) methods at varied basis set levels from 6‐31g to 6‐311++g (2d,2p). For comparison, we also used the second‐order Moller–Plesset Perturbation (MP2) method at the 6‐31+g(d) level. Twelve reasonable geometries on the potential energy hypersurface of serine and water system were considered with the global minimum, 10 of which are cyclic double‐hydrogen bonded structures and the other two are one‐hydrogen bonded structures. The optimized geometric parameters and interaction energies for various isomers at different levels were estimated. The infrared spectrum frequencies, IR intensities, and the vibrational frequency shifts are reported. Finally, the solvent effects on the geometries of the serine–water complexes were also investigated using self‐consistent reaction‐field (SCRF) calculations at the B3LYP/6‐311++g(d,p) level. The results indicate that the polarity of the solvent played an important role in the structures and relative stabilities of different isomers. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

Computational study of hydrogen bonding interaction between formamide and nitrosyl hydride

The hydrogen bonding interaction of formamide–nitrosyl hydride complex has been investigated using density functional theory (DFT) and ab initio method. The natural bond orbital (NBO) analysis and atom in molecules (AIM) theory were applied to understand the nature of the interaction. Two stable geometries are found on the potential energy surface, a six-membered cyclic structure of complex A and a seven-membered cyclic structure of complex B, characterized by AIM analysis. Complex A is less stable than complex B. It is confirmed that there are contractions of CH (compared with the monomer HCONH₂), NH bonds (compared with the monomer HNO) and the corresponding stretching vibrational frequencies are blue-shifted, while there is an elongation of the NH bond and the corresponding stretching vibrational frequency is red-shifted, relative to those of the monomer HCONH₂. From NBO analysis, it is evident that the electron densities in the σ^* (CH) and σ^*(NH) of the complex A are less than those of the monomers HCONH₂ and HNO, which strengthen CH and NH bonds. Furthermore, the increases in s-characters of X also strengthen XH bonds.     

A hydrogen pump: Transfer of four hydrogens from a cyclohexane ring to a triple bond during a menthofuran/bromoacetylene adduct rearrangement

The cycloadducts of menthofuran with acylbromoacetylenes, (3-bromo-1,6-dimethyl-5,6,7,8-tetrahydro-2H-2,4a-epoxynaphthalen-4-yl)(aryl)methanones, rearrange (CHCl₃, reflux, 1 h) to 2-(2-acylethyl)benzofurans (along with the expected 2-bromo-3-hydroxy-4,7-dimethyl-5,6,7,8-tetrahydronaphthalene-1-yl)(aryl)methanones) via 2-acylethynylmenthofurans, thus indicating the exceptionally mild and rapid transfer of four hydrogens from a cyclohexane ring to a triple bond through the furan moiety in the key intermediate 2-acylethynylmenthofuran.     

A Comparative Study of Hydrogen Bonding Using Density Functional Theory

The hydrogen‐bond energies of water dimer and water‐formaldehyde complexes have been studied using density functional theory (DFT). Basis sets up to aug‐cc‐pVXZ (X=D, T, Q) were used. It was found that counterpoise corrected binding energies using the aug‐cc‐pVDZ basis set are very close to those predicted with the aug‐cc‐pVQZ set. Comparative studies using various DFT functionals on these two systems show that results from B3LYP, mPW1PW91 and PW91PW91 functionals are in better agreements with those predicted using high‐level ab initio methods. These functionals were applied to the study of hydrogen bonding between guanine (G) and cytosine (C), and between adenine (A) and thy mine (T) base pairs. With the aug‐cc‐pVDZ basis set, the predicted binding energies of base pairs are in good agreement with the most elaborate ab initio results.     

Phase Equilibria of Hydrogen Bonding Fluid in a Slit Pore with Broken Symmetry

Phase equilibria of hydrogen bonding (HB) fluid confined in a slit pore with broken symmetry were investigated by the density functional theory incorporated with modified fundamental measure theory, where the symmetry breaking originated from the distinct interactions between fluid molecules and two walls of the slit pore. In terms of adsorption-desorption isotherms and the corresponding grand potentials, phase diagrams of HB fluid under various conditions are presented. Furthermore, through phase coexistences of laying transition and capillary condensation, the effects of HB interaction, pore width, fluid-pore interaction and the broken symmetry on the phase equilibrium properties are addressed. It is shown that these factors can give rise to apparent influences on the phase equilibria of confined HB fluid because of the competition between intermolecular interaction and fluid-pore interaction. Interestingly, a significant influence of broken symmetry of the slit pore is found, and thus the symmetry breaking can provide a new way to regulate the phase behavior of various confined fluids.     

Computational modeling of green hydrogen generation from photocatalytic H2S splitting: Overview and perspectives

Hydrogen plays an important role in developing a clean and sustainable future energy scenario. Substantial efforts to produce green hydrogen from water splitting, biomass and hydrogen sulfide (H₂S) have been made in recent years. H₂S, naturally occurring or generated in fuel gas processing and industrial wastewater treatment, can be split into hydrogen and sulfur via photocatalysis. Although it is not as widely used as water splitting for green hydrogen production, this process is considered to be an appropriate and sustainable way to meet the future energy demands, adding value to H₂S. Therefore, it is essential to understand how to improve the solar light utilization and splitting efficiency of H₂S based on the existing technology and materials. Along with that effort, molecular modeling and theoretical calculations are indispensable tools to provide guidance to effectively design photocatalysts for improving hydrogen generation efficiency. In this review, we summarize the published work on H₂S photocatalysis modeling and illustrate the use of different computational methods to gain more in-depth insight into the reaction mechanisms and processes. Moreover, an overview of quantum mechanical and molecular simulation approaches combined with other modeling techniques, relevant to material science and catalysis design and applicable to H₂S splitting is also presented. Challenges and future directions for developing H₂S splitting photocatalysts are highlighted in this contribution, which is intended to inspire further simulation developments and experiments for H₂S splitting, tailoring photocatalysts design towards highly efficient hydrogen production.     

Novel one-dimensional lanthanide acrylic acid complexes: an alternative chain constructed by hydrogen bonding

Novel one-dimensional (1D) chains of three lanthanide complexes La(L¹)₃(CH₃OH)]·CH₃OH (L¹=(E)-3-(2-hydroxyl-phenyl)-acrylic acid) 1, La(L²)₃(H₂O)₂]·2.75H₂O (L²=(E)-3-(3-hydroxyl-phenyl)-acrylic acid) 2, and La(L³)₃(CH₃OH)₂(H₂O)]·CH₃OH (L³=(E)-3-(4-hydroxyl-phenyl)-acrylic acid) 3 are reported. The crystal structure data are as follows for 1: C₂₉H₂₉LaO₁₁, monoclinic, P2₁/n, a=15.4289(12) Å, b=7.9585(6) Å, c=23.041(2) Å, β=99.657(2)°, Z=4, R₁=0.0637, wR₂=0.0919; for 2: C₂₇H_30.50LaO_13.75, triclinic, P−1, a=8.4719(17) Å, b=13.719(3) Å, c=14.570(3) Å, α=62.19(3)°, β=99.657(2)°, γ=78.22(3)°, Z=2, R₁=0.0384, wR₂=0.0820; and for 3: C₃₀H₃₅LaO₁₃, monoclinic, P2(1)/c, a=9.5667(6) Å, b=24.3911(15) Å, c=14.0448(9) Å, β=109.245(2)°, Z=4, R₁=0.0374, wR₂=0.0630. All the three structure data were collected using graphite monochromated molybdenum Kα radiation and refined using full-matrix least-squares techniques on F². These structures show that four kinds of the carboxylato bridge modes are included in these chains to link the La(III) ions. It is the first time that it has been found that the intra-chain hydrogen bonding can construct an alternative chain even, when the coordination bridge mode is the same along the chain (complex 2). There are 2D and 3D hydrogen bonding in the crystal lattices of complexes 1-3.     

Statistical theory for a hydrogen bonding fluid system of A a D d type (IV): Depletion potential between colloid particles

The depletion potential between two colloid particles immersed in a hydrogen bonding fluid has been investigated by density functional theory. The study is motivated by the wide applications of hydrogen bonding fluids in the field of colloid science, and the effects of relevant factors on the depletion potential and depletion force between colloid particles have been studied. These factors include the size ratio of the colloid particle to the fluid molecule, the bulk density of the fluid, the functionality (the number of proton acceptors a and proton donors d) and hydrogen bonding strength as well as the colloid-fluid interaction energy. By comparing the depletion potential calculated under various conditions, it is shown that the effects of these factors on the depletion potential are very significant, and in particular in regulating the depletion force and its range.     

Kilogram-scale synthesis of carbon quantum dots for hydrogen evolution,sensing and bioimaging

The development of large-scale synthetic methods for high quality carbon quantum dots (CQDs) is fundamental to their applications. However, the macroscopic preparation and scale up synthetic of CQDs is still in its infancy. Here, we report a facile, green, kilogram-scale synthesis of high quality fluorescent CQDs derived from poplar leaves via a one-step hydrothermal method. Notably, the throughput of CQDs can reach a level up to as high as 1.4975 kg in one pot. The structure and properties of the as-prepared CQDs were assessed through TEM, XRD, XPS and various spectroscopic methods. The obtained high quality CQDs with a photoluminescent quantum yield of 10.64% showed remarkable stability in aqueous media, rich functional groups, high photostability, consistent photoluminescence within biological pH range and low cytotoxicity. On account of these good properties, we demonstrated the multifunctional application to electrocatalytic water splitting, Fe³⁺ sensing and bioimaging. It showed remarkable electrocatalytic activity, Fe³⁺ sensitivity and good biocompatibility. This study provides a green, facile, inexpensive and large-scale method for producing high quality CQDs, which provides application value for large-scale production of CQDs.