London Dispersion Interactions Research Articles

Smoother Semiclassical Dispersion for Density Functional Theory via D3S: Understanding and Addressing Unphysical Minima in the D3 Dispersion Correction Model.

One of the most widely used and computationally efficient models that accounts for London dispersion interactions within density functional theory (DFT) is the D3 dispersion correction model. In this work, we demonstrate that this model can induce the appearance of unphysical minima on the potential energy surface (PES) when the coordination number of atoms changes. Optimizing to these artifactual structures can lead to significant errors in determining the interaction energy between two molecules and in estimating the thermodynamic properties of the system. In several specific examples, such as Kuratowski-type H2-NiKur and H2-PdKur clusters, these local minima exhibited extremely high PES curvature, resulting in incorrect estimations of harmonic frequencies and significant overestimations of zero-point energy and enthalpy values. Although such erroneous behavior of the D3 model is relatively rare, it can occur across a wide range of chemical species, including molecules like the [Li(C6H6)]+ complex and the dispiro(acridan)-substituted pyracene (DSAP) molecule. Our analysis reveals that the root of the problem lies in the definition of the AB atomic-pair dependent C6AB coefficients in the D3 model. To address this issue, we propose a reparameterization of the D3 model by introducing a modified C6AB functional form that now depends on the specific pair of considered atoms. This new model, termed D3-Smooth (or D3S for short), is designed to smooth out the PES associated with the dispersion correction. By doing so, we demonstrate that D3S eliminates unphysical local minima while maintaining the quite satisfactory accuracy of the parent D3 method in interaction energy benchmark sets. For example, the RMS difference between using the D3(BJ) correction to B3LYP and the D3S(BJ) correction across the large MGCDB84 data set of nearly 5000 data points is only 0.12 kJ/mol. Similar results are obtained for every other D3-corrected functional tested. Consistent with this result, no significant improvement could be obtained for the B3LYP-D3S(0) correction by reoptimizing the damping function.

Eliminating the Deadwood: A Machine Learning Model for CCS Knowledge-Based Conformational Focusing for Lipids.

Accurate elucidation of gas-phase chemical structures using collision cross section (CCS) values obtained from ion-mobility mass spectrometry benefits from a synergism between experimental and in silico results. We have shown in recent work that for a molecule of modest size with a proscribed conformational space we can successfully capture a conformation(s) that can match experimental CCS values. However, for flexible systems such as fatty acids that have many rotatable bonds and multiple intramolecular London dispersion interactions, it becomes necessary to sample a much greater conformational space. Sampling more conformers, however, accrues significant computational cost downstream in optimization steps involving quantum mechanics. To reduce this computational expense for lipids, we have developed a novel machine learning (ML) model to facilitate conformer filtering according to the estimated gas-phase CCS values. Herein we report that the implementation of our CCS knowledge-based approach for conformational sampling resulted in improved structure prediction agreement with experiment by achieving favorable average CCS prediction errors of ∼2% for lipid systems in both the validation set and the test set. Moreover, most of the gas-phase candidate conformations obtained by using CCS focusing achieved lower energy-minimum geometries than the candidate conformations without focusing. Altogether, the implementation of this ML model into our modeling workflow has proven to be beneficial for both the quality of the results and the turnaround time. Finally, while our approach is limited to lipids, it can be readily extended to other molecules of interest.

Lewis Acid-Base Pairs: The Bonding Rule of Closed-Shell M···M' Interactions (M = HgII/PdII; M' = AgI/AuI).

Metallophilic interactions are the widespread interactions in multimetal clusters to orientate closed-shell metal self-assembly form linear, facet, or block clusters. The closed-shell metal cation does not have empty valence orbitals, but is able to attract each other. It is still a conundrum to understand the resource in balancing the strong Coulomb repulsion between two cations. Most traditional descriptions attribute the counterintuitive attractions to London dispersion, Pauli repulsions, and ambiguous orbital interactions. However, neither the dispersion nor the unsourced donor-acceptor interaction can be applied to explain the saturability and directionality in multimetal clusters, where the M···M' structure is the basic molecular unit. Here, we clarify the origination of the covalency in closed-shell metallophilic interactions based on the study of heterobimetallic compounds composed of d10-d8 species (AgI/AuI-PdII) and d10-d10 species (AgI/AuI-HgII) obtained from experiments. The inner d electrons not only participate in the metallophilic interactions but also show different Lewis acidity and basicity in the formation of M···M' structures. The present work not only provides us a novel covalent perspective to visualize the closed-shell M···M' interactions but also unveils the truth of metallophilic interactions.

Correction: The major role of London dispersion interaction in the assembly of cellulose, chitin, and chitosan

Correction: The major role of London dispersion interaction in the assembly of cellulose, chitin, and chitosan

Polymorphism and White Light Emission of 1‐Bromo‐3,5,7‐triphenyladamantane Compared with 1,3,5,7‐Tetraphenyladamantane

AbstractHere we report our investigation of 1‐bromo‐3,5,7‐triphenyladamantane (1) and the elucidation of polymorphic crystals (1 A and 1 B) using single crystal X‐ray diffraction. In the monoclinic crystal system of 1 A (P21/n), we observed CH–π interactions, while Br⋅⋅⋅Br interactions are absent. Conversely, the Br⋅⋅⋅Br interactions are an apparent factor in the formation of the monoclinic crystal system of 1 B (R ). We compare our findings with 1,3,5,7‐tetraphenyladamantane (2), characterized by numerous CH–π interactions in the solid. Computational analyses were employed to investigate the interactions within the characteristic dimers present in the unit cells of 1 A and 1 B, including visualization of noncovalent interactions and the use of the atoms‐in‐molecules approach as well as MO analyses. These support the notion of London dispersion (LD) dimer‐dimer interactions in 1 A between the phenyl moieties, whereas 1 B exhibits additional dimer‐dimer Br⋅⋅⋅Br contacts. In contrast, the crystals of 2 are exclusively held together by CH–π stacking LD interactions, a feature absent in the polymorphs of 1. Both polymorphic forms of 1 emit white light when subjected to 900 nm continuous wave laser irradiation, displaying a subtle blue shift compared to 2. The absence of CH–π stacking interactions between the dimers of 1 causes a small red‐shift in the emission spectrum.

Correction: The major role of London dispersion interaction in the assembly of cellulose, chitin, and chitosan

Correction: The major role of London dispersion interaction in the assembly of cellulose, chitin, and chitosan

Pressure Induced Alteration and Stabilization of Intermolecular Stacking in Square-planar Osmium tetracarbonyl.

Osmium carbonyls are well known to form stable 18-electron complexes like Os(CO)5 , Os2 (CO)9 and Os3 (CO)12 having both bridging and terminal carbonyls. For osmium tetra-carbonyl, Os(CO)4 solid-state packing significantly alters the ground-state structure. The gas-phase stable see-saw geometry converts to a square-planar structure in solid state. Highly efficient intermolecular stacking between Os(CO)4 units assists this transformation. Each Os(CO)4 molecule is stacked in a staggered orientation with respect to each other. Pressure induces a [Xe]4f14 5d6 6s2 (S=2)→[Xe]4f14 5d8 (S=0) electronic transition in osmium stabilize a square planar osmium tetra-carbonyl. Under the influence of isotropic pressure, the molecules not only come closer to each other but their relative orientations also get significantly altered. Calculations show that at P=1 GPa and above, the eclipsed orientation for the intermolecular stacking gets preferred over the staggered form. The staggered→eclipsed intermolecular stacking orientation under pressure is shown to be controlled by London dispersion interactions.

Intramolecular London Dispersion Interactions in Single-Molecule Junctions.

This work shows the first example of using intramolecular London dispersion interactions to control molecular geometry and quantum transport in single-molecule junctions. Flexible σ-bonded molecular junctions typically occupy straight-chain geometries due to steric effects. Here, we synthesize a series of thiomethyl-terminated oligo(dimethylsilmethylene)s that bear [CH2-Si(CH3)2]n repeat units, where all backbone dihedral states are sterically equivalent. Scanning tunneling microscopy break-junction (STM-BJ) measurements and theoretical calculations indicate that in the absence of a strong steric bias concerted intramolecular London dispersion interactions staple the carbosilane backbone into coiled conformations that remain intact even as the junction is stretched to its breakpoint. As these kinked conformations are highly resistive to electronic transport, we observe record-high conductance decay values on an experimental junction length basis (β = 1.86 ± 0.12 Å-1). These studies reveal the potential of using intramolecular London dispersion interactions to design single-molecule electronics.

Iridium-Catalyzed Enantioselective Transfer Hydrogenation of 1,1-Dialkylethenes with Ethanol: Scope and Mechanism.

Despite half a century's advance in the field of transition-metal-catalyzed asymmetric alkene hydrogenation, the enantioselective hydrogenation of purely alkyl-substituted 1,1-dialkylethenes has remained an unmet challenge. Herein, we describe a chiral PCNOx-pincer iridium complex for asymmetric transfer hydrogenation of this alkene class with ethanol, furnishing all-alkyl-substituted tertiary stereocenters. High levels of enantioselectivity can be achieved in the reactions of substrates with secondary/primary and primary/primary alkyl combinations. The catalyst is further applied to the redox isomerization of disubstituted alkenols, producing a tertiary stereocenter remote to the resulting carbonyl group. Mechanistic studies reveal a dihydride species, (PCNOx)Ir(H)2, as the catalytically active intermediate, which can decay to a dimeric species (κ3-PCNOx)IrH(μ-H)2IrH(κ2-PCNOx) via a ligand-remetalation pathway. The catalyst deactivation under the hydrogenation conditions with H2 is much faster than that under the transfer hydrogenation conditions with EtOH, which explains why the (PCNOx)Ir catalyst is effective for the transfer hydrogenation but ineffective for the hydrogenation. The suppression of di-to-trisubstituted alkene isomerization by regioselective 1,2-insertion is partly responsible for the success of this system, underscoring the critical role played by the pincer ligand in enantioselective transfer hydrogenation of 1,1-dialkylethenes. Moreover, computational studies elucidate the significant influence of the London dispersion interaction between the ligand and the substrate on enantioselectivity control, as illustrated by the complete reversal of stereochemistry through cyclohexyl-to-cyclopropyl group substitution in the alkene substrates.

Advances and Prospects in Understanding London Dispersion Interactions in Molecular Chemistry.

London dispersion (LD) interactions are the main contribution of the attractive part of the van der Waals potential. Even though LD effects are the driving force for molecular aggregation and recognition, the role of these omnipresent interactions in structure and reactivity had been largely underappreciated over decades. However, in the recent years considerable efforts have been made to thoroughly study LD interactions and their potential as a chemical design element for structures and catalysis. This was made possible through a fruitful interplay of theory and experiment. This review highlights recent results and advances in utilizing LD interactions as a structural motif to understand and utilize intra- and intermolecularly LD-stabilized systems. Additionally, we focus on the quantification of LD interactions and their fundamental role in chemical reactions.

Advances and Prospects in Understanding London Dispersion Interactions in Molecular Chemistry

AbstractLondon dispersion (LD) interactions are the main contribution of the attractive part of the van der Waals potential. Even though LD effects are the driving force for molecular aggregation and recognition, the role of these omnipresent interactions in structure and reactivity had been largely underappreciated over decades. However, in the recent years considerable efforts have been made to thoroughly study LD interactions and their potential as a chemical design element for structures and catalysis. This was made possible through a fruitful interplay of theory and experiment. This review highlights recent results and advances in utilizing LD interactions as a structural motif to understand and utilize intra‐ and intermolecularly LD‐stabilized systems. Additionally, we focus on the quantification of LD interactions and their fundamental role in chemical reactions.

Binary conformers of a flexible, long-chain fluoroalcohol: dispersion controlled selectivity and relative abundances in a jet.

The complex conformational panorama of binary 4,4,4-trifluoro-1-butanol (TFB) aggregates was investigated using chirped-pulse Fourier transform microwave spectroscopy, aided by conformational searches using CREST (Conformer-Rotamer Ensemble Sampling Tool) and quantum chemistry calculations. From nearly 1500 initial dimer geometries, 16 most stable binary candidates were obtained within a relative energy window of ∼4 kJ mol-1. Rotational spectra of five binary conformers were experimentally observed in supersonic expansion and assigned. Interestingly, three out of the five observed binary conformers are composed solely of monomer conformers, which were not observed in their isolated gas phase forms in jet expansion. In addition, an observed dimer that is made exclusively of the most stable TFB monomer subunits does not correspond to the global minimum. The intricate kinetically and thermodynamically controlled dimer formation mechanisms are discussed, and a modified kinetic-thermodynamic model was developed, providing conformational abundances that are in good agreement with the experiment. Subsequent non-covalent interaction analyses reveal that the observed conformers are held together by one primary O-H⋯O hydrogen bond and secondary intermolecular C-H⋯O, C-H⋯F, and/or O-H⋯F interactions, as well as C-H⋯H-C London dispersion interactions between the methylene groups. Further symmetry-adapted perturbation theory analyses of the TFB dimer conformers and related alcohol dimers reveal a considerable rise in dispersion contributions with increasing n-alkyl carbon chain length and highlight the role of dispersion interactions in preferentially stabilizing the global minimum of the TFB dimer.

Molecular Wind-Up Meter for the Quantification of London Dispersion Interactions.

ConspectusThe experimental quantification of interactions on the molecular level provides the necessary basis for the design of functional materials and chemical processes. The interplay of multiple parameters and the small quantity of individual interactions pose a special challenge for such endeavors. The common method is the use of molecular balances, which can exist in two different states. Thereby, a stabilizing interaction can occur in one of the states, favoring its formation and thus affecting the thermodynamic equilibrium of the system. One challenge is determining the change in this equilibrium since various analytical methods could not be applied to fast-changing equilibria. A new and promising method for quantifying molecular interactions is the use of Molecular Wind-up Meters (MWM) in which the change in kinetics, rather than the effect on thermodynamics, is investigated. An MWM is transformed with an energy input (e.g. irradiation) into a metastable state. Then, the rate of thermal transformation back to the ground state is measured. The strength of interactions present in the metastable state controls the kinetics of the back reactions, allowing direct correlation. The advantage of this approach lies in the high sensitivity (energy differences can be larger by 1 order of magnitude) and, in general, allows the use of a broader range of solvents and analytical methods. An Azobenzene-based MWM has been established as a powerful tool to quantify London dispersion interactions. London dispersion (LD) represents the attractive part of the van der Waals potential. Although neglected in the past due to its weak character, it has been shown that the influence of LD on the structure, stability, and reactivity of matter can be decisive. Especially in larger molecules, its energy contribution increases overproportionately with the number of atoms, which has sparked increasing interest in the use of so-called dispersion energy donors (DED) as a new structural element. Application of the azobenzene-based MWM not only allowed the differentiation of bulkiness, but also systematically addressed the influence of the length of n-alkyl chains. Additionally, the solvent influence on LD was studied. Based on the azobenzene MWM, an increment system has been proposed, allowing a rough estimate of the effect of a specific DED.

Dispersion Interactions in Condensed Phases and inside Molecular Containers.

ConspectusThe past decade has seen significant progress in the understanding and appreciation of the importance of London dispersion interactions (LDIs) in supramolecular systems and solutions. The Slater-Kirkwood formula relates LDIs to the molecular polarizabilities of the two interacting molecular species (α) and their interaction distance (a dependence of R-6). When advancing arguments related to intermolecular interactions, it is frequently assumed that molecules with larger molecular polarizabilities are more amenable to larger LDIs. However, arguments related to molecular polarizabilities are not always transferable to the condensed phase. In fact, the underlying bulk and molecular polarizabilities of common solvents show opposing trends. The intuitive concept that aromatic molecules are more polarizable than saturated hydrocarbons and that perfluorinated molecules are less polarizable than saturated hydrocarbons applies to the condensed phase only. When treating association phenomena in solution, where LDIs are generally very attenuated, the use of bulk polarizabilities is recommended, which are experimentally accessible through either refractive index measurements or suitable solvatochromic probes. Such probes can also be used to assess polarizabilities inside molecular container compounds, such as cucurbit[n]urils (CBn), cyclodextrins, calixarenes, and hemicarcerands. These macrocyclic cavities can have extreme microenvironments. For example, the inner concave phase of CB7 has been shown to be weakly polarizable, falling in between the gas phase and perfluorohexane; those of β-cyclodextrin and p-sulfonatocalix[4]arene have been found to be similarly polarizable as water and alkanes, respectively, and the inside of hemicarcerands displays a very large bulk polarizability, exceeding that of diiodomethane. CBn compounds are privileged molecular container compounds, which we exemplify in this Account through case studies. (1) CBn macrocycles are prime water-soluble receptors for hydrocarbons, allowing for the reduction of the binding free energies to two components: the hydrophobic effect and dispersion interactions. To understand hydrocarbon binding, we initiated the HYDROPHOBE challenge, which revealed the shortcomings of both quantum-chemical and molecular dynamics approaches. (2) The smallest CBn receptor, CB5, is uniquely suited to bind the entire noble gas series, where hydrophobic effects and dispersion interactions operate in opposite directions. CB5 was revaled to be a unique synthetic receptor for noble gases, with the dominant driving force being the recovery of the cavitation energies for the hydration of noble gases in aqueous solution. Computational methods that encounter challenges in predicting hydrocarbon affinities and trends for CB6 and CB7 perform well for noble gases binding to CB5. (3) The larger homologue, CB8, allows one to set up intermolecular interaction chambers by the encapsulation of a (first) aromatic guest, thereby tuning LDIs inside the receptor cavity. In this manner, CB8 can be modulated to preferentially bind unsaturated and aromatic rather than saturated hydrocarbons, while the unmodified cavities of the smaller macrocycles CB6 and CB7 show selective binding of saturated hydrocarbons. (4) The (charged) host-guest complexes of CBn hosts are sufficiently stable in the gas phase, allowing for the study of the influence of LDIs on inner-phase chemical reactions. These studies are particularly interesting for the theoretical analysis of isolated host-guest LDIs, as experimental and computational data are directly comparable in the gas phase due to the absence of the solvation effect.

Accelerating σ-Bond Metathesis at Sn(II) Centers.

Molecular main-group hydride catalysts are attractive as cheap and Earth-abundant alternatives to transition-metal analogues. In the case of the latter, specific steric and electronic tuning of the metal center through ligand choice has enabled the iterative and rational development of superior catalysts. Analogously, a deeper understanding of electronic structure-activity relationships for molecular main-group hydrides should facilitate the development of superior main-group hydride catalysts. Herein, we report a modular Sn-Ni bimetallic system in which we systematically vary the ancillary ligand on Ni, which, in turn, tunes the Sn center. This tuning is probed using Sn L1 XAS as a measure of electron density at the Sn center. We demonstrate that increased electron density at Sn centers accelerates the rate of σ-bond metathesis, and we employ this understanding to develop a highly active Sn-based catalyst for the hydroboration of CO2 using pinacolborane. Additionally, we demonstrate that engineering London dispersion interactions within the secondary coordination sphere of Sn allows for further rate acceleration. These results show that the electronics of main-group catalysts can be controlled without the competing effects of geometry perturbations and that this manifests in substantial reactivity differences.

Phase-Dependence of Molecular Structures Arising from Weak London Dispersion Interactions.

ConspectusThe structures of molecules can be different in different phases. Intermolecular forces, even those of weak noncovalent interactions (WNCIs), can lead to a preference for quite different conformations in the solid, the gas, and the liquid phases. WNCIs can cause variations in bond lengths, angles, and torsional angles. Since structure is a fundamental concept in chemistry, the knowledge of structural changes with phase is important to understand the source and effects of distorting contributions from WNCIs but also as a predictive tool for the design and stabilization of new bonding situations.X-ray crystallography is ubiquitous and now mostly straightforward to perform, but facilities for the determination of accurate gas-phase structure determination are rare, and gas-phase work is laborious and time-consuming. There are currently about 1.25 million crystal structures and more than 12 500 experimental gas-phase structures, but the intersection of the two data sets that can tell us about the structural differences of the same molecule in different phases is surprisingly small.In this Account, we describe several cases of WNCI-dominated systems for which accurate experimental structure determinations exist for both the gas phase and the solid state and, in one case, also for solution. The examples include aryl-aryl, aryl-alkyl, and alkyl-alkyl interactions; systems with chalcogen and halogen bonding; and fluorine-based interactions in arylboranes. We work out the role of WNCIs in stabilizing large, strained, or sterically overloaded molecules. We will show how flexible molecules will fold under the action of WNCIs when isolated in the gas and how they fold or unfold when they are embedded in an environment of neighbors in crystals. We will show how they can vary in strength when the substitution patterns in aryl groups are changed by different halogens and how intramolecular WNCIs, such as those forming rings, change when such systems experience additional intermolecular WNCIs.Overall, we hope that this Account will give the reader an idea of the type and magnitude of structural changes that can be expected from a free molecule in the gas phase or a single molecule calculated by quantum chemistry compared with one embedded in a crystal. This should define the limits of comparability and provide some predictive concepts of the distortions and variations to be expected.

The major role of London dispersion interaction in the assembly of cellulose, chitin, and chitosan

The major role of London dispersion interaction in the assembly of cellulose, chitin, and chitosan

Catalytic Asymmetric Hydrogen Atom Transfer: Enantioselective Hydroamination of Alkenes.

We report a highly enantioselective radical-based hydroamination of enol esters with sulfonamides jointly catalyzed by an Ir photocatalyst, Brønsted base, and tetrapeptide thiol. This method is demonstrated for the formation of 23 protected β-amino-alcohol products, achieving selectivities up to 97:3 er. The stereochemistry of the product is set through selective hydrogen atom transfer from the chiral thiol catalyst to a prochiral C-centered radical. Structure-selectivity relationships derived from structural variation of both the peptide catalyst and olefin substrate provide key insights into the development of an optimal catalyst. Experimental and computational mechanistic studies indicate that hydrogen-bonding, π-π stacking, and London dispersion interactions are contributing factors for substrate recognition and enantioinduction. These findings further the development of radical-based asymmetric catalysis and contribute to the understanding of the noncovalent interactions relevant to such transformations.

London Dispersion Interactions Imitate Pressure for Molecular Crystals.

The packing of molecular crystals, in which the constituent molecular units have no directional forces, is primarily controlled by weak London dispersion (LD) forces. These forces assist in stabilizing the system by bringing the molecular units into the proximity of each other. In this paper, the same effect is shown to be externally induced by pressure. The minimal pressure required to correctly describe the crystal structure without LD interactions (PLD) provides a quantifiable measure for the weak intermolecular interactions. LD forces are shown to be essential for an accurate description of the pressure-induced phase transitions across examples of linear, trigonal-planar, square-planar, tetrahedral, trigonal bipyramidal, and octahedral molecules.

London Dispersion Effects on the Stability of Heavy Tetrel Molecules.

London dispersion (LD) interactions, which stem from long-range electron correlations arising from instantaneously induced dipoles can occur between neighboring atoms or molecules, for example, between H atoms within ligand C-H groups. These interactions are currently of interest as a new method of stabilizing long bonds and species with unusual oxidation states. They can also limit reactivity by installing LD enhanced groups into organic frameworks or ligand substituents. Here, we address the most recent advances in the design of LD enhanced ligands, the sterically counterintuitive structures that can be generated and the consequences that these interactions can have on the structures and reactivity of sterically crowded heavy group 14 species.