Cation-pi interactions with a model for the side chain of tryptophan: structures and absolute binding energies of alkali metal cation-indole complexes

Threshold collision-induced dissociation techniques are employed to determine bond dissociation energies (BDEs) of mono- and bis-complexes of alkali metal cations, Li+, Na+, K+, Rb+, and Cs+, with indole, C8H7N. The primary and lowest energy dissociation pathway in all cases is endothermic loss of an intact indole ligand. Sequential loss of a second indole ligand is observed at elevated energies for the bis-complexes. Density functional theory calculations at the B3LYP/6-31G level of theory are used to determine the structures, vibrational frequencies, and rotational constants of these complexes. Theoretical BDEs are determined from single point energy calculations at the MP2(full)/6-311+G(2d,2p) level using the B3LYP/6-31G* geometries. The agreement between theory and experiment is very good for all complexes except Li+ (C8H7N), where theory underestimates the strength of the binding. The trends in the BDEs of these alkali metal cation-indole complexes are compared with the analogous benzene and naphthalene complexes to examine the influence of the extended pi network and heteroatom on the strength of the cation-pi interaction. The Na+ and K+ binding affinities of benzene, phenol, and indole are also compared to those of the aromatic amino acids, phenylalanine, tyrosine, and tryptophan to elucidate the factors that contribute to the binding in complexes to the aromatic amino acids. The nature of the binding and trends in the BDEs of cation-pi complexes between alkali metal cations and benzene, phenol, and indole are examined to help understand nature's preference for engaging tryptophan over phenylalanine and tyrosine in cation-pi interactions in biological systems.     

Effect of metal ions (Li+, Na+, K+, Mg2+, Ca2+, Ni2+, Cu2+, and Zn2+) and water coordination on the structure of glycine and zwitterionic glycine

Interactions between metal ions and amino acids are common both in solution and in the gas phase. Here, the effect of metal ions and water on the structure of glycine is examined. The effect of metal ions (Li+, Na+, K+, Mg2+, Ca2+, Ni2+, Cu2+, and Zn2+) and water on structures of Gly.Mn+(H2O)m and GlyZwitt.Mn+(H2O)m (m = 0, 2, 5) complexes have been determined theoretically by employing the hybrid B3LYP exchange-correlation functional and using extended basis sets. Selected calculations were carried out also by means of CBS-QB3 model chemistry. The interaction enthalpies, entropies, and Gibbs energies of eight complexes Gly.Mn+ (Mn+ = Li+, Na+, K+, Mg2+, Ca2+, Ni2+, Cu2+, and Zn2+) were determined at the B3LYP density functional level of theory. The computed Gibbs energies DeltaG degrees are negative and span a rather broad energy interval (from -90 to -1100 kJ mol(-1)), meaning that the ions studied form strong complexes. The largest interaction Gibbs energy (-1076 kJ mol(-1)) was computed for the NiGly2+ complex. Calculations of the molecular structure and relative stability of the Gly.Mn+(H2O)m and GlyZwitt.Mn+(H2O)m (Mn+ = Li+, Na+, K+, Mg2+, Ca2+, Ni2+, Cu2+, and Zn2+; m = 0, 2, and 5) systems indicate that in the complexes with monovalent metal cations the most stable species are the NO coordinated metal cations in non-zwitterionic glycine. Divalent cations Mg2+, Ca2+, Ni2+, Cu2+, and Zn2+ prefer coordination via the OO bifurcated bonds of the zwitterionic glycine. Stepwise addition of two and five water molecules leads to considerable changes in the relative stability of the hydrated species. Addition of two water molecules at the metal ion in both Gly.Mn+ and GlyZwitt.Mn+ complexes reduces the relative stability of metallic complexes of glycine. For Mn+ = Li+ or Na+, the addition of five water molecules does not change the relative order of stability. In the Gly.K+ complex, the solvation shell of water molecules around K+ ion has, because of the larger size of the potassium cation, a different structure with a reduced number of hydrogen-bonded contacts. This results in a net preference (by 10.3 kJ mol(-1)) of the GlyZwitt.K+H2O5 system. Addition of five water molecules to the glycine complexes containing divalent cations Mg2+, Ca2+, Ni2+, Cu2+, and Zn2+ results in a net preference for non-zwitterionic glycine species. The computed relative Gibbs energies are quite high (-10 to -38 kJ mol(-1)), and the NO coordination is preferred in the Gly.Mn+(H2O)5 (Mn+ = Mg2+, Ca2+, Ni2+, Cu2+, and Zn2+) complexes over the OO coordination.     

Gas-Phase Reactions of hydrated alkaline earth metal ions, M2+(H2O) n (M = Mg, Ca, Sr, Ba and n = 4–7), with benzene

Gas-phase reactions of hydrated divalent alkaline earth metal ions and benzene were investigated by electrospray ionization Fourier-transform mass spectrometry. Rate constants for solvent-exchange reactions were determined as a function of hydration extent for Mg2+, Ca2+, Sr2+, and Ba2+ clusters containing four to seven water molecules each. All of the strontium and barium clusters react quickly with benzene. Barium reacts slightly faster than the corresponding strontium cluster with the same number of water molecules attached. For calcium, clusters with four and five water molecules react quickly, whereas those with six and seven water molecules do not. Magnesium with four water molecules reacts quickly, but not when five through seven water molecules are attached. The slow reactivity observed for some of these clusters indicates that the cation-pi interaction between the metal ion and benzene is partially screened by the surrounding water molecules. The reactivity of magnesium with seven water molecules is intermediate that of the hexa- and pentahydrate and the tetrahydrate. This result is consistent with the seventh water molecule being in the outer shell and much more weakly bound. The unusual trend in reactivity observed for magnesium may be due to the presence of mixed shell structures observed previously. These results are the first to provide information about the relative importance of cation-pi interactions in divalent metal ions as a function of metal hydration extent. Such studies should also provide a model and some insight into the relative binding affinities of divalent metal ions to aromatic residues on peptides and proteins.     

Ab initio molecular orbital calculations on ion pair-water complexes of metal halides and oxides

Ab initio MO calculations are performed on a series of ion-molecular and ion pair-molecular complexes of H₂O + MX (MX = LiF, LiCl, NaCl, BeO and MgO) systems. BSSE-corrected stabilization energies, optimized geometrical parameters, internal force constants and harmonic vibrational frequencies have been evaluated for all the structures of interest. The trends observed in the geometrical parameters and other properties calculated for the mono-hydrated contact ion pair complexes parallel those computed for the complexes of the individual ions. The bifurcated structures are found to be saddle points with an imaginary frequency corresponding to the rocking mode of water molecules. The solventshared ion pair complexes have high interaction energies. Trends in the internal force constant and harmonic frequency values are discussed in terms of ion-molecular and ion-pair molecular interactions.     

Influence of the d orbital occupation on the nature and strength of copper cation-pi interactions: threshold collision-induced dissociation and theoretical studies

Threshold collision-induced dissociation techniques are employed to determine the bond dissociation energies of a wide variety of copper cation-pi complexes, Cu(+)(pi-ligand), where pi-ligand = benzene, flurobenzene, chlorobenzene, bromobenzene, iodobenzene, phenol, toluene, anisole, pyrrole, N-methylpyrrole, indole, naphthalene, aniline, N-methylaniline, and N,N-dimethylaniline. The primary and lowest energy dissociation pathway corresponds to the endothermic loss of the intact neutral pi-ligand for all complexes except those to N-methylpyrrole, indole, aniline, N-methylaniline, and N,N-dimethylaniline. In the latter complexes, the primary dissociation pathway corresponds to loss of the intact ligand accompanied by charge transfer, thereby producing a neutral copper atom and ionized pi-ligand. Fragmentation of the pi-ligands is also observed at elevated energies in several cases. Theoretical calculations at the B3LYP/6-311G(d,p) level of theory are used to determine the structures, vibrational frequencies, and rotational constants of these complexes. Multiple low-energy conformers are found for all of the copper cation-pi complexes. Theoretical bond dissociation energies are determined from single point energy calculations at the B3LYP/6-311+G(3df,2p) level of theory using the B3LYP/6-311G(d,p) optimized geometries. The agreement between theory and experiment is very good for most complexes. The nature and strength of the binding in these copper cation-pi complexes are studied and compared with the corresponding cation-pi complexes to Na(+). Natural bond orbital analyses are carried out to examine the influence of the d orbital occupation on copper cation-pi interactions.     

Structures and energetics of the cation-pi interactions of Li+, Na+, and K+ with cup-shaped molecules: effect of ring addition to benzene and cavity selectivity

The interactions of alkali metal cations (Li (+), Na (+), and K (+)) with the cup-shaped molecules, tris(bicyclo[2.2.1]hepteno)benzene and tris(7-azabicyclo[2.2.1]hepteno)benzene have been investigated using MP2(FULL)/6-311+G(d,p)//MP2/6-31G(d) level of theory. The geometries and interaction energies obtained for the metal ion complexation with the cup-shaped systems trindene and benzotripyrrole are compared with the results for benzene-metal ion complexes to examine the effect of ring addition to the benzene on structural and binding affinities. The cup-shaped molecules exhibit two faces or cavities (top and bottom). Except for one of the conformers of tris(7-azabicyclo[2.2.1]hepteno)benzene), the metal ions prefer to bind with the top face over bottom face of the cup-shaped molecules. The selectivity of the top face is due to strong interaction of the cation with the pi cloud not only from the central six-membered ring but also from the pi electrons of rim C=C bonds. In contrast, the metal ions under study exhibit preference to bind with the bottom face rather than top face of tris(7-azabicyclo[2.2.1]hepteno)benzene) when the lone pair of electrons of three nitrogen atoms participates in binding with metal ions. This bottom face selectivity could be ascribed to the combined effect of the cation-pi and strong cation-lone pair interactions. As evidenced from the values of pyramidalization angles, the host molecule becomes deeper bowl when the lone pair of electrons of nitrogen atoms participates in binding with cation. Molecular electrostatic potential surfaces nicely explain the cavity selectivity in the cup-shaped systems and the variation of interaction energies for different ligands. Vibrational frequency analysis is useful in characterizing different metal ion complexes and to distinguish top and bottom face complexes of metal ions with the cup-shaped molecules.     

Theoretical Studies on the Interaction between Metal Cations and Cytosine, Guanine

1 INTRODUCTION The study on the interaction between metal cations and biomacromolecules is one of the important subjects of bioinorganic chemistry. As is well known, the metal ions play an important role in keeping the basic structures and realizing the normal functions of biomacromolecules like proteins, nucleic acid, and peptide hormone[1]. However, at present the interac- tion mechanism has not been understood yet. In recent years remarkable achievements have been obtained in this fie…     

The role of cation-pi interactions in biomolecular association. Design of peptides favoring interactions between cationic and aromatic amino acid side chains.

Cation-pi interactions between amino acid side chains are increasingly being recognized as important structural and functional features of proteins and other biomolecules. Although these interactions have been found in static protein structures, they have not yet been detected in dynamic biomolecular systems. We determined, by (1)H NMR spectroscopic titrations, the energies of cation-pi interactions of the amino acid derivative AcLysOMe (1) with AcPheOEt (2) and with AcTyrOEt (3) in aqueous and three organic solvents. The interaction energy is substantial; it ranges from -2.1 to -3.4 kcal/mol and depends only slightly on the dielectric constant of the solvent. To assess the effects of auxiliary interactions and structural preorganization on formation of cation-pi interactions, we studied these interactions in the association of pentapeptides. Upon binding of the positively-charged peptide AcLysLysLysLysLysNH(2) (5) to the negatively-charged partner AcAspAspXAspAspNH(2) (6), in which X is Leu (6a), Tyr (6b), and Phe (6c), multiple interactions occur. Association of the two pentapeptides is dynamic. Free peptides and their complex are in fast exchange on the NMR time-scale, and 2D (1)H ROESY spectra of the complex of the two pentapeptides do not show intermolecular ROESY peaks. Perturbations of the chemical shifts indicated that the aromatic groups in peptides 6b and 6c were affected by the association with 5. The association constants K(A) for 5 with 6a and with 6b are nearly equal, (4.0 +/- 0.7) x 10(3) and (5.0 +/- 1.0) x 10(3) M(-)(1), respectively, while K(A) for 5 with 6c is larger, (8.3 +/- 1.3) x 10(3) M(-)(1). Molecular-dynamics (MD) simulations of the pentapeptide pairs confirmed that their association is dynamic and showed that cation-pi contacts between the two peptides are stereochemically possible. A transient complex between 5 and 6 with a prominent cation-pi interaction, obtained from MD simulations, was used as a template to design cyclic peptides C(X) featuring persistent cation-pi interactions. The cyclic peptide C(X) had a sequence in which X is Tyr, Phe, and Leu. The first two peptides do, but the third does not, contain the aromatic residue capable of interacting with a cationic Lys residue. This covalent construct offered conformational stability over the noncovalent complexes and allowed thorough studies by 2D NMR spectroscopy. Multiple conformations of the cyclic peptides C(Tyr) and C(Phe) are in slow exchange on the NMR time-scale. In one of these conformations, cation-pi interaction between Lys3 and Tyr9/Phe9 is clearly evident. Multiple NOEs between the side chains of residues 3 and 9 are observed; chemical-shift changes are consistent with the placement of the side chain of Lys3 over the aromatic ring. In contrast, the cyclic peptide C(Leu) showed no evidence for close approach of the side chains of Lys3 and Leu9. The cation-pi interaction persists in both DMSO and aqueous solvents. When the disulfide bond in the cyclic peptide C(Phe) was removed, the cation-pi interaction in the acyclic peptide AC(Phe) remained. To test the reliability of the pK(a) criterion for the existence of cation-pi interactions, we determined residue-specific pK(a) values of all four Lys side chains in all three cyclic peptides C(X). While NOE cross-peaks and perturbations of the chemical shifts clearly show the existence of the cation-pi interaction, pK(a) values of Lys3 in C(Tyr) and in C(Phe) differ only marginally from those values of other lysines in these dynamic peptides. Our experimental results with dynamic peptide systems highlight the role of cation-pi interactions in both intermolecular recognition at the protein-protein interface and intramolecular processes such as protein folding.     

The special five-membered ring of proline: An experimental and theoretical investigation of alkali metal cation interactions with proline and its four- and six-membered ring analogues

The interaction of the alkali metal cations, Li+, Na+, and K+, with the amino acid proline (Pro) and its four- and six-membered ring analogues, azetidine-2-carboxylic acid (Aze) and pipecolic acid (Pip), are examined in detail. Experimentally, threshold collision-induced dissociation of the M+(L) complexes, where M = Li, Na, and K and L = Pro, Aze, and Pip, with Xe are studied using a guided ion beam tandem mass spectrometer. From analysis of the kinetic energy dependent cross sections, M(+)-L bond dissociation energies are measured. These analyses account for unimolecular decay rates, internal energy of reactant ions, and multiple ion-molecule collisions. Ab initio calculations for a number of geometric conformations of the M+(L) complexes were determined at the B3LYP/6-311G(d,p) level with single-point energies calculated at MP2(full), B3LYP, and B3P86 levels using a 6-311+G(2d,2p) basis set. Theoretical bond energies show good agreement with the experimental bond energies, which establishes that the zwitterionic form of the alkali metal cation/amino acid, the lowest energy conformation, is formed in all cases. Despite the increased conformational mobility in the Pip systems, the Li+, Na+, and K+ complexes of Pro show higher binding energies. A meticulous examination of the zwitterionic structures of these complexes provides an explanation for the stability of the five-membered ring complexes.     

碱(土)金属离子与2-(3′-羟基-2′-吡啶基)苯并噁唑阳离子-π复合物及其分子内质子转移过程的理论研究

采用密度泛函B3LYP方法,在6-311++G(d,p)基组水平上对碱(土)金属离子(Li+,Na+,K+,Be2+,Mg2+和Ca2+)与2-(3’-羟基-2’-吡啶基)苯并噁唑(HPyBO)的36种阳离子-π复合物的初始构型进行了几何全优化,并计算了其相互作用能.结果表明,碱(土)金属离子与HPyBO复合物有较强的阳离子-π相互作用,部分复合物甚至达到了化学键的强度.相对能量的变化表明碱(土)金属离子的作用能改变HPyBO分子内质子转移过程的能垒,甚至可以导致优势构型反转.当考虑水的溶剂效应后,各质子转移异构体的相对能量及质子转移的能垒均有一定程度的改变.另外,应用分子中的原子(AIM)方法对复合物分子内氢键的键临界点性质进行了分析.     

Influence of the water molecule on cation-pi interaction: ab initio second order Møller-Plesset perturbation theory (MP2) calculations

The influence of introducing water molecules into a cation-pi complex on the interaction between the cation and the pi system was investigated using the MP2/6-311++G method to explore how a cation-pi complex changes in terms of both its geometry and its binding strength during the hydration. The calculation on the methylammonium-benzene complex showed that the cation-pi interaction is weakened by introducing H(2)O molecules into the system. For example, the optimized interaction distance between the cation and the benzene becomes longer and longer, the transferred charge between them becomes less and less, and the cation-pi binding strength becomes weaker and weaker as the water molecule is introduced one by one. Furthermore, the introduction of the third water molecule leads to a dramatic change in both the complex geometry and the binding energy, resulting in the destruction of the cation-pi interaction. The decomposition on the binding energy shows that the influence is mostly brought out through the electrostatic and induction interactions. This study also demonstrated that the basis set superposition error, thermal energy, and zero-point vibrational energy are significant and needed to be corrected for accurately predicting the binding strength in a hydrated cation-pi complex at the MP2/6-311++G level. Therefore, the results are helpful to better understand the role of water molecules in some biological processes involving cation-pi interactions.     

Computational study of the interaction of indole-like molecules with water and hydrogen sulfide

The characteristics of the interaction between water and hydrogen sulfide with indole and a series of analogs obtained by substituting the NH group of indole by different heteroatoms have been studied by means of ab initio calculations. In all cases, minima were found corresponding to structures where water and hydrogen sulfide interact by means of X-H···π contacts. The interaction energies for all these π complexes are quite similar, spanning from -13.5 to -18.8 kJ/mol, and exhibiting the stability sequence NH > CH(2) ≈ PH > Se ≈ S > O, for both water and hydrogen sulfide. Though interaction energies are similar, hydrogen sulfide complexes are slightly favored over their water counterparts when interacting with the π cloud. σ-Type complexes were also considered for the systems studied, but only in the case of water complexes this kind of complexes is relevant. Only for complexes formed by water and indole, a significantly more stable σ-type complex was found with an interaction energy amounting to -23.6 kJ/mol. Oxygen and phosphorous derivatives also form σ-type complexes of similar stability as that observed for π ones. Despite the similar interaction energies exhibited by complexes with water and hydrogen sulfide, the nature of the interaction is very different. For π complexes with water the main contributions to the interaction energy are electrostatic and dispersive contributing with similar amounts, though slightly more from electrostatics. On the contrary, in hydrogen sulfide complexes dispersion is by far the main stabilizing contribution. For the σ-type complexes, the interaction is clearly dominated by the electrostatic contribution, especially in the indole-water complex.     

Ligand-stabilized aromatic three-membered gold rings and their sandwichlike complexes

Electronic structure calculations (DFT) suggest that ligand-stabilized three-membered gold(I) rings constituting the core structure in a series of cyclo-Au3L(n)H(3-n) (L = CH3, NH2, OH and Cl; n = 1, 2, 3) molecules exhibit aromaticity, which is primarily due to 6s and 5d cyclic electron delocalization over the triangular Au3 framework (s- and d-orbital aromaticity). The aromaticity of the novel triangular gold(I) isocycles was verified by a number of established criteria of aromaticity. In particular, the nucleus-independent chemical shift, NICS(0), the upfield changes in the chemical shifts for Li+, Ag+, and Tl+ cations over the Au3 ring plane, and their interaction with electrophiles (e.g., H+, Li+, Ag+, and Tl+) are indicative for the aromaticity of the three-membered gold(I) rings. Interestingly, unlike the respective substituted derivatives of cyclopropenium cation and the bora-cyclopropene carbacyclic analogues, the aromatic Au3 rings, although exhibit comparable diatropicity, react with electrophiles in a different way affording 1:1 and 2:1 sandwichlike complexes. The bonding in the three-membered gold(I) rings is characterized by a common ring-shaped electron density, more commonly seen in aromatic organic molecules and in "all-metal" aromatics, such as the cyclo-[Hg3]4- tetraanion. Moreover, the cation-pi interactions in the 1:1 and 1:2 sandwichlike complexes formed upon reacting the Au3 rings with electrophiles, depending on the nature of the cation, are predicted to be predominantly electrostatic (Li+, Tl+) or covalent (H+, Ag+). The 1:2 complexes constitute a new class of sandwichlike complexes, which are expected to have novel properties and applications.     

Density Functional Theory Study on Hydrogen Bonding Interaction of Catechin-(H2O)n

Density functional theory B3LYP method with 6‐31G* basis set has been used to optimize the geometries of the catechin, water and catechin‐(H₂O)_n complexes. The vibrational frequencies have been studied at the same level to analyze these complexes. Six and eleven stable structures for the catechin‐H₂O and catechin‐(H₂O)₂ have been found, respectively. Theories of atoms in molecules (AIM) and natural bond orbital (NBO) have been utilized to investigate the hydrogen bonds involved in all the systems. The interaction energies of all the complexes corrected by basis set superposition error, are from ?13.27 to ?83.56 kJ/mol. All calculations also indicate that there are strong hydrogen‐bonding interactions in catechin‐water complexes. The strong hydrogen‐bonding contributes to the interaction energies dominantly. The O–H stretching motions in all the complexes are red‐shifted relative to that of the monomer.     

醇及脱氧核糖与水分子间三体作用强度的快速准确计算

快速准确预测醇及脱氧核糖分子与水形成的氢键复合物的三体作用强度, 对准确模拟水环境下蛋白质和DNA的结构和功能至关重要. 基于对多体极化作用的理解, 在可极化偶极-偶极作用模型(PBFF)基础上, 将体系中的极性化学键视为化学键偶极, 通过模拟键偶极的极化计算了醇及脱氧核糖与水分子形成的氢键复合物的三体作用能. 通过拟合甲醇与水氢键复合物的三体作用能随分子间距离变化的能量曲线确定了所需的参数. 将模型和所确定的参数应用于计算更多的甲醇、 乙醇及脱氧核糖与水氢键复合物的三体作用能, 检验了模型的准确性和参数的可转移性. 计算结果表明, 可极化偶极-偶极作用模型及所确定的参数能够较好地预测具有不同结构的氢键复合物的三体作用强度, 其精度可与MP2方法的计算精度相当.     

Free-energy calculations of protein-ligand cation-pi and amino-pi interactions: from vacuum to proteinlike environments

To probe the role of cation-pi and amino-pi interactions in the context of protein-ligand interactions, the stability of 55 X-ray cation/amino-pi motifs involving the Ade moieties of cofactor molecules and Arg, Lys, Asn, or Gln side chains of their host protein was evaluated using quantum chemistry calculations. The conjunction of vacuum interaction energies, vibrational entropy, and solvation contributions led to identify Arg-Ade as the most favorable cation/amino-pi complex in the solvents considered, followed by Asn/Gln-Ade and Lys-Ade: their minimum interaction free energies are approximately equal to -7, -4, and -2 kcal/mol, respectively, in the solvents of dielectric constant similar to that estimated for proteins (i.e., acetone, THF, and CCl(4)). Remarkably, these free-energy values of cation/amino-pi interactions correlate well with their frequency of occurrences in protein-ligand structures, which corroborates our approach in the absence of experimental data.     

Hydration energies of sodiated amino acids from gas-phase equilibria determinations

The sequential hydration of a number of sodiated amino acids is investigated using a high-pressure mass spectrometer. Ions produced continuously by electrospray are injected into the reaction chamber in the pulsed mode where the hydration equilibria, AANa+(H2O)n-1+H2O=AANa+(H2O)n (AA=Val, Pro, Met, Phe, and Gln), and the temperature dependence of the equilibrium constants are measured in the gas phase at 10 mbar (N2 bath gas and known pressure of H2O). The thermochemical properties, DeltaH degrees n, DeltaS degrees n, and DeltaG degrees n, for the hydrated systems are determined and discussed in conjunction with the structural forms. The results show that the binding energies of water to the AANa+ complexes decrease with the increasing number of water molecules. The present results from equilibrium measurements are compared to those from earlier studies obtained by other techniques. A correlation between the free energy changes for the addition of the first and second water molecules to AANa+, and the corresponding sodium ion affinities, is observed. Generally, the hydration free energy becomes weaker as the AA-Na+ bond strength increases.     

Ab initio study of ternary radical–molecule complexes between HCN(HNC) and HO(HS) species

MP2 calculations with the cc-pVTZ basis set were used to analyze the intermolecular interactions in ternary radical–molecule complexes between HCN(HNC) and HO(HS) species, in gas phase and in water media. Particular attention was given to parameters such as the cooperative energies and many-body interaction energies. The results indicate that hydrogen bonding between two HCN(HNC) molecules gives more stability to triads than hydrogen bonding between HCN(HNC) and OH(SH) species. The electronic properties of the complexes were analyzed using the parameters derived from the atoms in molecules methodology. The water media has an enhancing influence on the stabilities of studied clusters versus the ones obtained in gas phase.     

Assessment of density functionals and force field methods on anion–π interaction in heterocyclic calix complexes

The performance of ten density functionals and four force field methods in describing non-covalent interactions have been assessed by studying the interaction energies and structures of the four anion–π complexes involving tetraoxacalix[2]arene[2]triazine and various anions. Their structures are optimized at MP2/6-311++G(d,p) level, and interaction energies are obtained at DF-MP2-F12/aug-cc-pVDZ level. The result shows that the functional M06-2X predicts the most reliable interaction energy, followed by wB97XD and BHandH. B97D slightly overestimates the interaction energy. Other functionals and force field methods seriously overestimate the interaction energy. For the structures, three functionals M06-2X, wB97XD and BH and H predict the most reliable results, followed by B97D. The force field methods predict the largest deviations. The present work suggests that the functional M06-2X is a reliable method to describe energies and structural properties of the large molecules involving the anion–π interactions.