Mapping the correlations between bandgap, HOMO, and LUMO trends for meta substituted Zn-MOFs.

Bandgap is a key property that determines electrical and optical properties in materials. Modulating the bandgap thus is critical in developing novel materials particularly semiconductors with improved features. This study examines the bandgap, highest occupied molecular orbital (HOMO), and lowest unoccupied molecular orbital (LUMO) energy level trends in a metal organic framework, metal-organic framework 5 (MOF-5), as a function of Hammett substituent effect (with the constant σm in the meta-position of the benzene ring) and solvent dielectric effect (with the constant ε). Specifically, experimental design and response surface methodologies helped to assess the significance of trends and correlations between these molecular properties with σm and ε. While the HOMO and LUMO decrease with increasing σm, the LUMO exhibits greater sensitivity to the substituent's electron withdrawing capability. The relative difference in these trends helps to explain why the bandgap tends to decrease with increasing σm.

Monovalent cation binding to model systems and the macrocyclic depsipeptide, emodepside.

This study focuses on the systematic exploration of the emodepside conformations bound to monovalent K+ ion using quantum mechanical density functional theory (DFT) calculations at the M06-2X/6-31+G(d,p) level of theory. Nine conformers of emodepside and their complexes with K+ ion were characterized as stationary points on the potential energy surface. The conformational isomers were examined for their 3D structures, bonding, energetics, and interactions with the cation. A cavitand-like structure (CC) is identified to be the energetically most stable arrangement. To arrive at a better understanding of the K+ ion binding, calculations were initially performed on complexes formed by the K+ and Na+ ions with model ligands (methyl ester and N,N-dimethyl acetamide). Both the natural bond orbital (NBO) method and the block-localized wavefunction (BLW) energy decomposition approach was employed to assess the bonding and energetic contributions stabilizing the ion-bound model complexes. Finally, the solvent effect was evaluated through complete geometry optimizations and energy minimizations for the model ion-ligand complexes and the emodepside-K+ bound complexes using an implicit solvent model mimicking water and DMSO.

Conformational Preference of Lithium Polysulfide Clusters Li2Sx (x = 4-8) in Lithium-Sulfur Batteries.

Structures are of fundamental importance for diverse studies of lithium polysulfide clusters, which govern the performance of lithium-sulfur batteries. The ring-like geometries were regarded as the most stable structures, but their physical origin remains elusive. In this work, we systematically explored the minimal structures of Li2Sx (x = 4-8) clusters to uncover the driving force for their conformational preferences. All low-lying isomers were generated by performing global searches using the ABCluster program, and the ionic nature of the Li···S interactions was evidenced with the energy decomposition analysis based on the block-localized wave function (BLW-ED) approach and further confirmed with the quantum theory of atoms in molecule (QTAIM). By analysis of the contributions of various energy components to the relative stability with the references of the lowest-lying isomers, the controlling factor for isomer preferences was found to be the polarization interaction. Notably, although the electrostatic interaction dominates the binding energies, it contributes favorably to the relative stabilities of most isomers. The Li+···Li+ distance is identified as the key geometrical parameter that correlates with the strength of the polarization of the Sx2- fragment imposed by the Li+ cations. Further BLW-ED analyses reveal that the cooperativity of the Li+ cations primarily determines the relative strength of the polarization.

Planar Four-Membered Diboron Actinide Compound with Double Möbius Aromaticity.

The Möbius rule predicts that a planar four-membered metallacycle can be aromatic with four mobile electrons, but such a simple ring has escaped recognition because it usually favors Hückel anti-aromaticity. Here, we report that a quasi-square four-membered actinide compound (Pa2B2) is doubly Möbius aromatic. Chemical bonding analyses reveal that this diboron protactinium molecule has four delocalized π electrons in addition to four delocalized σ electrons, satisfying the 4n Möbius rule for both σ and π components. Energetically, the block-localized wavefunction method, which is the simplest variant of ab initio valence bond theory, shows that the delocalization energy for the π and σ electrons reaches up to 65.0 and 72.3 kcal/mol, respectively, while the extra cyclic resonance energy (ECRE) amounts to 45 kcal/mol. The large positive ECRE values strongly confirm the unprecedented double Möbius aromaticity in Pa2B2. We anticipate that this new type of aromatic molecule can enrich the concept of Möbius aromaticity and open a new avenue for actinide compounds.

The strength and selectivity of perfluorinated nano-hoops and buckybowls for anion binding and the nature of anion-π interactions.

Perfluorinated cycloparaphenylenes (F-[n]CPP, n = 5-8), boron nitride nanohoop (F-[5]BNNH), and buckybowls (F-BBs) were proposed as anion receptors via anion-π interactions with halide anions (Cl- , Br- and I- ), and remarkable binding strengths up to -294.8 kJ/mol were computationally verified. The energy decomposition approach based on the block-localized wavefunction method, which combines the computational efficiency of molecular orbital theory and the chemical intuition of ab initio valence bond theory, was applied to the above anion-π complexes, in order to elucidate the nature and selectivity of these interactions. The overall attraction is mainly governed by the frozen energy component, in which the electrostatic interaction is included. Remarkable binding strengths with F-[n]CPPs can be attributed to the accumulated anion-π interactions between the anion and each conjugated ring on the hoop, while for F-BBs, additional stability results from the curved frameworks, which distribute electron densities unequally on π-faces. Interestingly, the strongest host was proved to be the F-[5]BNNH, which exhibits the most significant anisotropy of the electrostatic potential surface due to the difference in the electronegativities of nitrogen and boron. The selectivity of each host for anions was explored and the importance of the often-overlooked Pauli exchange repulsion was illustrated. Chloride anion turns out to be the most favorable anion for all receptors, due to the smallest ionic radius and the weakest destabilizing Pauli exchange repulsion.

Selectivity Rule of Cryptands for Anions: Molecular Rigidity and Bonding Site.

Cryptands utilize inside CH or NH groups as hydrogen bond (H-bond) donors to capture anions such as halides. In this work, the nature and selectivity of confined hydrogen bonds inside cryptands were computationally analyzed with the energy decomposition scheme based on the block-localized wavefunction method (BLW-ED), aiming at an elucidation of governing factors in the binding between cryptands and anions. It was revealed that the intrinsic strengths of inward hydrogen bonds are dominated by the electrostatic attraction, while the anion preferences (selectivity) of inner CH and NH hydrogen bonds are governed by the Pauli exchange repulsion and electrostatic interaction, respectively. Typical conformers of cages are classified into two groups, including the C3(h) -symmetrical conformers, in which all halide anions are located near the centroids of cages, and the "semi-open" conformers, which exhibit shifted bonding sites for different halide anions. Accordingly, the difference in governing factors of selectivity is attributed to either the rigidity of cages or the binding site of anions for these two groups. In details, the C3 conformers of NH cryptands can be enlarged more remarkably than the C3(h) -symmetrical conformers of CH cryptands as the size of anion (ionic radius) increases, resulting in the relaxation of the Pauli repulsion and a dramatic reduction in electrostatic attraction, which eventually rules the selectivity of NH cryptands for halide anions. By contrary, the CH cryptands are more rigid and cannot effectively reduce the Pauli repulsion, which subsequently governs the anion preference. Unlike C3 conformers whose rigidity determines the selectivity, semi-open conformers exhibit different binding sites for different anions. From F- to I- , the bonding site shifts toward the outside end of the pocket inside the semi-open NH cryptand, leading to the significant reduction of the electrostatic interaction that dominates the anion preference. Differently, binding sites are much less affected by the size of anion inside the semi-open CH cryptand, in which the Pauli exchange repulsion remains the key factor for the selectivity of inner hydrogen bonds.

Stretched Central Double Bonds in Dialumene and Disilene by Amino Substituents: A Case of Lone Pair Repulsion.

There have been remarkable advances in the syntheses and applications of groups 13 and 14 homonuclear ethene analogues. However, successes are largely limited to aryl- and/or silyl-substituted species. Analogues bearing two or more heteroatoms are still scarce. In this work, the block-localized wavefunction (BLW) method at the density functional theory (DFT) level was employed to study dialumene and disilene bearing two amino substituents whose optimal geometries exhibit significantly stretched central M=M (M=Al or Si) double bonds compared with aryl- and/or silyl-substituted species. Computational analyses showed that the repulsion between the lone electron pairs of amino substituents and M=M π bond plays a critical role in the elongation of the M=M bonds. Evidently, replacing the substituent groups -NH2 with -BH2 can enhance the planarity and shorten the central double bonds due to the absence of lone pair electrons in BH2 .

Captodative Effect Facilitates the Excitation in Diboron Molecule (CAAC)2 B2 (SH)2.

Given the extraordinary versatility in chemical reactions and applications, boron compounds have gained increasing attentions in the past two decades. One of the remarkable advances is the unprecedented preparation of unsaturated boron species. Notably, Braunschweig et al. found that the cyclic (alkyl)(amino) carbenes (CAACs) stabilized diboron molecules (CAAC)2 B2 (SR)2 host unpaired electrons and exist in the 90°-twisted diradical form, while other analogues, such as N-heterocyclic carbenes (NHCs), stabilized diboron molecules prefer a conventional B=B double bond. Since previous studies recognized the differences in the steric effect between CAAC and NHC carbenes, here we focused on the role of thiol substituents in (CAAC)2 B2 (SR)2 by gradually localizing involved electrons. The co-planarity of the thiol groups and the consequent captodative effect were found to be the culprit for the 90°-twisted diradical form of (CAAC)2 B2 (SR)2 . Computational analyses identified two forces contributing to the π electron movements. One is the "push" effect of lone pairs on the sulfur atoms which boosts the π electron delocalization between the BB center and CAACs. The other is the π electron delocalization within each (CAAC)B(SR) fragment where the pull effect originates from the π electron withdrawal by CAACs. There are two such independent and orthogonal push-pull channels which function mainly in individual (CAAC)B(SR) fragments. This enhanced π push-pull effect in the triplet state facilitates the electronic excitation in (CAAC)2 B2 (SR)2 by reducing the singlet-triplet gap.

On the nature of inter-anion coinage bonds.

To explore the binding energy profiles and elucidate the bonding nature in counter-intuitive anion⋯anion coinage bonds (CiBs), thirty-one complexes were constructed, and the inter-anion CiBs were studied theoretically. The metastability was evidenced by the characteristic potential wells in six cases, demonstrating that anions [Au(CN)4]-, [Ag(CN)2]- and [AuO]- are appropriate building blocks for CiBs. The kinetic stability was further supported by ab initio molecular dynamics (AIMD) simulations and the analyses based on the local vibrational mode and quantum theory of atoms in molecules (QTAIM) methods. The anion⋯anion CiBs in the dimers of [AuCl4]- and [Au(CN)4]- previously observed in condensed phases were confirmed to be thoroughly repulsive under vacuum, but turned attractive in the crystal environment which was simulated using the solvation model based on density (SMD). However, the intrinsic strength of the inter-anion bonding is barely variated by the environment, as it is the combination of the inter-anion interaction and the environment effect that stabilizes the anion pairs. The block-localized wavefunction (BLW) method and its corresponding energy decomposition (BLW-ED) approach were further employed aiming at a chemically meaningful explanation for these counterintuitive phenomena. By inspecting the profiles of energy components, we identified the vital distinction between inter-anion CiBs and conventional non-covalent interactions lying in the electrostatic interaction, which variates nonmonotonically in the inter-anion complexes. The electrostatic interaction also dominates the depth of potential wells, which is commonly used to evaluate the kinetic stability, while Pauli exchange repulsion is the most repulsive factor preventing the formation of anion adducts. The importance of the Pauli exchange repulsion was further highlighted by comparing cases with and without metastability, in which the absence of a potential well is solely caused by the enhancement of the Pauli exchange repulsion.

Partial Double Metal-Carbon Bonding Model in Transition Metal Methyl Compounds.

The chemical bond between a transition metal and a methyl group (M-CH3) is typically defined as a single covalent bond, which is of fundamental significance and general interest in understanding the structural properties and reactivity of transition metal alkyl compounds. Herein, we demonstrate that the M-CH3 bonding involves varying σ and π components and thus should be best described in terms of the partial double M═CH3 bond. The often-neglected π bonding stems from an occupied π-symmetric orbital of the methyl group comprising all three C-H σ bonds (but one C-H' contributes more than the other two) and a vacant low-lying metal d(π) orbital, and is associated with the intramolecular C-H'···M agostic effect (i.e., an acute M-C-H' angle and a short H'···M distance), whose origin is still controversial. We quantify the geometric and energetic impacts of the π interaction involved in the M-CH3 bond by explicitly computing the intramolecular πCH' → dM interaction with the ab initio valence bond (VB) theory. Our computations of the ligand-free [TiCH3]3+ and a series of metallocene catalysts provide a direct proof for the presence of the π bonding in M-CH3 bonds, which is the cause for the agostic effect. The partial double M═CH3 bonding model is not only validated by a range of bonding analyses including VB self-consistent field (VBSCF)-based energy decomposition and quantum theory of atoms in molecules (QTAIM) but also authenticated by the specific activity of double M═CH3 bonds in the C-H activation and olefin insertion. More importantly, the σ bond gradually switches from a classical covalent bond to a novel charge-shift bond with the π bonding becoming increasingly significant. We anticipate that the recognition of the π interaction between electrophilic metal centers and C-H bonds can benefit the understanding of the nature of metal-carbon bonds in transition metal ethyl, alkyl, and carbene compounds.

Evidence for πCHR→dM bonding in transition metal carbene compounds (LnMCHR) and its decisive role in the α-agostic effect.

It has been generally recognized that the α-agostic interaction (M⋯H-C) in transition metal carbene compounds LnMCHR (R = H, Me etc.) can be interpreted with a double metal-carbon bonding model. This bonding model involves the reorganization of the σ component, which can be illustrated in terms of three-center two-electron (3c-2e) M-H-C covalent bond as in transition metal alkyl compounds. Herein, we propose an alternative partial triple metal-carbon bonding model to elucidate the agostic interaction in LnMCHR. Apart from the well-defined σ and π bonds, there exists a seemingly weak but decisive third force, namely the πCHR→dM bonding between an occupied π-like symmetric CHR orbital and a vacant metal d orbital, which is the true origin of the α-agostic effect. This partial triple bonding model is authenticated on both Fischer- and Schrock-type carbenes by an ab initio valence bond (VB) method or the block-localized wavefunction (BLW) method, which has the capability to quantify this notable π bonding and further demonstrate its geometric, energetic and spectral impacts on agostic transition metal carbene compounds. We also show that ancillary ligands can modulate the πCHR→dM bonding through electronic and steric effects.

On the Bonding Nature in the Crystalline Tri-Thorium Cluster: Core-Shell Syngenetic σ-Aromaticity.

A unique thorium-thorium bond was observed in the crystalline tri-thorium cluster [{Th(η8 -C8 H8 )(µ3 -Cl)2 }3 {K(THF)2 }2 ]∞ , though the claim of σ-aromaticity for Th3 bond has been questioned. Herein, a new type of core-shell syngenetic bonding model is proposed to describe the stability of this tri-thorium cluster. The model involves a 3c-2e bond in the Th3 core and a multicentered (ThCl2 )3 charge-shift bond with 12 electrons scattering along the outer shell. To differentiate the strengths of the 3c-2e bond and the charge-shift bond, the block-localized wavefunction (BLW) method which falls into the ab initio valence bond (VB) theory is employed to construct a strictly core/shell localized state and its contributing covalent resonance structure for the Th3 core bond. By comparing with the σ-aromatic H3 + and nonaromatic Li3 + , the computed resonance energies and extra cyclic resonance energies confirm that this Th3 core bond is truly delocalized and σ-aromatic.

Planar Tetracoordinate Silicon in Organic Molecules As Carbenoid-Type Amphoteric Centers: A Computational Study.

Designing and synthesizing a stable compound with a planar tetracoordinate silicon (ptSi) center is a challenging goal for chemists. Here, a series of potential aromatic ptSi compounds composed of four conjugated rings shared by a centrally embedded Si atom are theoretically designed and computationally verified. Both Born-Oppenheimer molecular dynamics (BOMD) simulations and potential energy surface scannings verify the high stability and likely existence of these compounds, particularly Si-16-5555 (SiN4 C8 H8 ) with 16 π electrons, under standard ambient temperature and pressure. Notably, the Hückel aromaticity rule, which works well for single rings, is inconsistent with the high stability of Si-16-5555 where the 16 p electrons are spread over four five-membered rings fused together. Bonding analyses show that the strong electron donation from the peripheral 12-membered conjugated ring with 16 π electrons to the vacant central atomic orbital Si 3pz leads to the stabilization for both the ptSi coordination and planar aromaticity. The partial occupation of Si 3pz results in the peculiar carbenoid-type behaviors for the amphoteric center. By modulating the electron density on the ring with substituent groups, we can regulate the nucleophilic and electrophilic properties of the central Si.

Hydrogen and Halogen Bonding in Homogeneous External Electric Fields: Modulating the Bond Strengths.

Recent years have witnessed various fascinating phenomena arising from the interactions of noncovalent bonds with homogeneous external electric fields (EEFs). Here we performed a computational study to interpret the sensitivity of intrinsic bond strengths to EEFs in terms of steric effect and orbital interactions. The block-localized wavefunction (BLW) method, which combines the advantages of both ab initio valence bond (VB) theory and molecular orbital (MO) theory, and the subsequent energy decomposition (BLW-ED) approach were adopted. The sensitivity was monitored and analyzed using the induced energy term, which is the variation in each energy component along the EEF strength. Systems with single or multiple hydrogen (H) or halogen (X) bond(s) were also examined. It was found that the X-bond strength change to EEFs mainly stems from the covalency change, while generally the steric effect rules the response of H-bonds to EEFs. Furthermore, X-bonds are more sensitive to EEFs, with the key difference between H- and X-bonds lying in the charge transfer interaction. Since phenylboronic acid has been experimentally used as a smart linker in EEFs, switchable sensitivity was scrutinized with the example of the phenylboronic acid dimer, which exhibits two conformations with either antiparallel or parallel H-bonds, thereby, opposite or consistent responses to EEFs. Among the studied systems, the quadruple X-bonds in molecular capsules exhibit remarkable sensitivity, with its interaction energy increased by -95.2 kJ mol-1 at the EEF strength 0.005 a.u.

Resonance-Assisted but Antielectrostatic Intramolecular Au···H-O Hydrogen Bonding in Gold(I) Complexes: A Computational Verification.

The peculiar Au···H hydrogen bonding has garnered significant interests, but its existence and nature remain an open question in gold chemistry. In this paper, we established and authenticated the first intramolecular Au···H-O hydrogen bonding in gold(I) complexes. Our computational results based on an ab initio valence bond (VB) method, namely the block-localized wave function (BLW) method, clarified that this Au···H-O hydrogen bonding is a new type of resonance-assisted hydrogen bond (RAHB). In this RAHB, π conjugation in the hydrogen bond donor has the capability to modulate the Au···H-O hydrogen bonding. In contrast to conventional RAHBs, however, the Au···H-O hydrogen bonding is antielectrostatic and is dominated by the charge transfer interaction including cooperative σ electron donation from the d orbital of the metal center to the antibonding orbital of the hydroxyl group and π conjugation from the hydroxyl group to adjacent π deficient or strong π electron withdrawing groups. This novel theoretical perspective not only confirms the existence and reveals the nature of intramolecular Au···H hydrogen bonding but also provides a promising strategy to rationally design strong gold hydrogen bonds.

Molecular magnetism in nanodomains of isoreticular MIL-88(Fe)-MOFs.

Molecular magnetism in nanodomains of three isoreticular MIL-88(Fe) analogues is studied and reported. Microstructures of isoreticular extended frameworks of MIL-88B, MIL-88C, and the interpenetrated analogue of MIL-88D, i.e., MIL-126, with the trigonal prismatic 6-c acs net are synthesized by linking Fe3O inorganic cluster units with organic carboxylate linkers - benzene-1,4-dicarboxylic acid (BDC), 2,6-naphthalene dicarboxylic acid (NDC), and biphenyl-4,4'-dicarboxylic acid (BPDC), using a controlled solvent driven self-assembly process followed by a solvothermal method. The powder XRD traces are matched with the simulated diffraction patterns generated from their corresponding crystal structures, revealing the hexagonal symmetry for MIL-88B and MIL-88C, and the tetragonal symmetry for MIL-126. The elemental composition analysis confirms the empirical formula to be Fe3O(L)3 where L is the organic linker, supporting the formation of isoreticular MIL-88(Fe)-MOFs with MIL-88 topology. The morphologies of microstructures analyzed by SEM and TEM exhibit long spindle shaped rods with a core and a shell-like architecture for MIL-88B and MIL-88 C whereas MIL-126 shows cubic-shaped microstructures. The M-T plots confirm their blocking temperatures, TB, to be 60 K, 50 K, and 40 K for MIL-88B, MIL-88C, and MIL-126, respectively. The M-H plots reveal their magnetic response to be ferromagnetic at 10 K with the coercivities, HC, ranging from 250 G to 180 G. The gradual decrease in the TB and HC correlates with the nanocrystals' domain size, which decreases from MIL-88B to MIL-88C to MIL-126. Their phase transition from the ferromagnetic state to the short range ordering of the superparamagnetic state is observed in the temperature range of 100 K to 300 K. At T > TB, nanocrystals of all three MIL-88 microstructures act as a single-magnetic domain, owing to their shape anisotropy and finite-dimensionality. The electron density distribution and the spin density state modeled for each MIL-88 analogue exhibit localized electron density and spin density on Fe3O clusters, indicating the short range magnetic moment ordering in triangular metal oxide nodes with no extended magnetic cooperativity from their organic linkers. The short-range ordering of superparamagnetism in MIL-88(Fe)-MOFs suggests their further study as porous molecular-based magnets.

Metalloradical complex Co-C˙Ph3 catalyzes the CO2 reduction in gas phase: a theoretical study.

Metal-stabilized radicals have been increasingly exploited in modern organic synthesis. Here, we theoretically designed a metalloradical complex Co-C˙Ph3 with the triplet characters through the transition metal cobalt (Co0) coordinating a triphenylmethyl radical. The potential catalytic role of this novel metalloradical in the CO2 reduction with H2/CH4 in the gas phase was explored via density functional theory (DFT) calculations. For the CO2 reduction reaction with H2, there are two possible pathways: one (path A) is the activation of CO2 by Co-C˙Ph3, followed by the hydrogenation of CO2. The other (path B) starts from the splitting of the H-H bond by Co-C˙Ph3, leading to the transition-metal hydride complex CoH-H, which can reduce CO2. DFT computations show that path B is more favorable than path A as their rate-determining free energy barriers are 18.3 and 27.2 kcal mol-1, respectively. However, for the reduction of CO2 by CH4 two different products, CH3COOH and HCOOCH3, can be generated following different reaction routes. Both routes begin with one CH4 molecule approaching the metalloradical Co-C˙Ph3 to form the intermediate CoH-CH3. This intermediate can evolve following two different pathways, depending on whether the H bonded to Co is transferred to the O (pathway PO) or the C (pathway PC) of CO2. Comparing their rate-determining steps, we identified that the PO route is more favorable for the reduction of CO2 by CH4 to CH3COOH with the reaction barrier 24.5 kcal mol-1. Thus, the present Co0-based metalloradical system represents a viable catalytic protocol that can contribute to the effective utilization of small molecules (H2 and CH4) to reduce CO2, and provides an alternative strategy for the exploration of CO2 conversion.

Role of Charge Transfer in Halogen Bonding.

Halogen bonding has received intensive attention recently for its applications in the construction of supramolecular assemblies and crystal engineering and its implications and potentials in chemical and biological processes and rational drug design. Peculiarly, in intermolecular interactions, halogen atoms are known as electron-donating groups carrying partial negative charges in molecules due to its high electronegativity, but they can counterintuitively act as Lewis acids and bind with Lewis bases in the form of a halogen bond. The unsettling issue regarding the nature of the halogen bonding is whether the electrostatics or charge transfer interaction dominates. The recently proposed σ-hole concept nicely reinforces the role of electrostatic attraction. Also, good correlations between the halogen bonding strength and the interaction energy from the simple point-charge model have been found. This leads to the claim that there is no need to invoke the charge transfer concept in the halogen bond. But there is alternative evidence supporting the importance of charge transfer interaction. Here, we visited a series of prominent halogen bonded complexes of the types Y3C-X···Z (X = Br, I; Y = F, Cl, Br; Z = F-, Cl-, Br-, I-, NMe3) with the block-localized wave function (BLW) method at the M06-2X-D3/6-311+G(d,p) (def2-SVP for iodine) level of theory. As the simplest variant of ab initio valence bond (VB) theory, the BLW method is unique in the strict localization of electrons within interacting moieties, allowing for quantitative evaluation of the charge transfer effect on geometries, spectral properties, and energetics in halogen bonding complexes. By comparing the halogen bonding complexes with and without the charge transfer interaction, we proved that the charge transfer interaction significantly shortens the X···Z bonding distance and stretches the C-X bonds. But the shortening of the halogen bonding results in the less favorable steric effect, which is composed of Pauli repulsion, electrostatics, and electron correlation. There are approximate linear correlations between the charge transfer effect and binding energy and between bonding distance and binding energy. These correlations may lead to the illusion that the charge transfer interaction is unimportant or irrelevant, but further analyses showed that the inclusion of charge transfer is critical for the proper description of the halogen bonding, as considering only electrostatics and polarization leads to only about 45-60% of the binding strengths and much elongated bonding distances.

Classical Electrostatics Remains the Driving Force for Interanion Hydrogen and Halogen Bonding.

Interanion hydrogen bonding (IAHB) and halogen bonding (IAXB) have emerged as a counterintuitive linker in a range of fascinating applications. Despite the overall repulsive (positive) binding energy, anions are trapped in a local minimum with its corresponding transition state (TS) preventing dissociation. In other words, the adduct of anions is metastable. Seemingly, the electrostatic paradigm and force field description of hydrogen/halogen bonding (HB/XB) are challenged, because of the preconceived Coulombic repulsion. Aiming at an insightful understanding of these interanion phenomena, we employed the energy decomposition approach based on the block-localized wavefunction method (BLW-ED) to investigate a series of exemplary interanion complexes. As expected, the key distinction from the conventional HB/XB lies in the electrostatic interaction, which is not increasingly repulsive as anions gradually approach to each other. Rather, there is a Coulombic barrier at a certain point. After this point, the electrostatic repulsion diminishes with the decreasing distance between anions. Differently, other energy components vary monotonically just like in conventional cases. The nonmonotonic characteristic of the electrostatic interaction in interanion complexes was reproduced using the multipole expansion in AMOEBA polarizable force field in which the state-specified atomic multipoles were adopted. This suggests that the nonmonotonicity can be well interpreted by classical electrostatic theory and there is no conceptual difference between conventional HB/XB and IAHB/IAXB. The stability of IAHB/IAXB depends on the competition between the local attractive HB/XB and the global Coulombic repulsion of net charges, though there is cooperativity between these two contrasting forces. This concise model was supported by the attractive IAHB/IAXB in modified molecular capsules, which exhibit strong quadruple HB/XBs and a considerable distance between charged substituents.

Inter-anion chalcogen bonds: Are they anti-electrostatic in nature?

Inter-anion hydrogen and halogen bonds have emerged as counterintuitive linkers and inspired us to expand the range of this unconventional bonding pattern. Here, the inter-anion chalcogen bond (IAChB) was proposed and theoretically analyzed in a series of complexes formed by negatively charged bidentate chalcogen bond donors with chloride anions. The kinetic stability of IAChB was evidenced by the minima on binding energy profiles and further supported by ab initio molecular dynamic simulations. The block-localized wave function (BLW) method and its subsequent energy decomposition (BLW-ED) approach were employed to elucidate the physical origin of IAChB. While all other energy components vary monotonically as anions get together, the electrostatic interaction behaves exceptionally as it experiences a Coulombic repulsion barrier. Before reaching the barrier, the electrostatic repulsion increases with the shortening Ch⋯Cl- distance as expected from classical electrostatics. However, after passing the barrier, the electrostatic repulsion decreases with the Ch⋯Cl- distance shortening and subsequently turns into the most favorable trend among all energy terms at short ranges, representing a dominating force for the kinetic stability of inter-anions. For comparison, all energy components exhibit the same trends and vary monotonically in the conventional counterparts where donors are neutral. By comparing inter-anions and their conventional counterparts, we found that only the electrostatic energy term is affected by the extra negative charge. Remarkably, the distinctive (nonmonotonic) electrostatic energy profiles were reproduced using quantum mechanical-based atomic multipoles, suggesting that the crucial electrostatic interaction in IAChB can be rationalized within the classical electrostatic theory just like conventional non-covalent interactions.