Contrasting preferences of N and P substituted heteroaromatics towards metal binding: probing the regioselectivity of Li+ and Mg2+ binding to (CH)6−m−nNmPn

Abstract

High level ab initio and hybrid DFT methods have been employed to investigate the interactions of metal ions (Li(+) and Mg(2+)) with N and P substituted six membered heteroaromatics (CH)(6-m-n)N(m)P(n). The binding energy (BE) of metal ions with the N and P substituted heteroaromatics has been computed at the CCSD(T)/cc-pVTZ//MP2/cc-pVTZ level with counterpoise correction. In the present study we systematically examined the preferential modes of binding of metal ions to the heteroaromatics. N-Substituted heteroaromatics show a strong preference for cation-σ mode of binding whereas the P-substituted heteroaromatics prefer cation-π mode of binding with the metal ions. Energy decomposition analysis (EDA) using the DFT-SAPT scheme has been carried out to analyse the contribution of various energy components to the BE. The results illustrate that for the cation-π complexes, the contribution of the induction term is more whereas in the case of cation-σ there is a competition between induction and electrostatic terms in the interaction energy.

Impact of the Chirality and Curvature of Carbon Nanostructures on Their Interaction with Aromatics and Amino Acids

“…Several experimental and computational studies have been performed to explore the binding strengths of different amino acids on the surfaces of CNTs and graphene. [23,24] The importance of aromatic content for the interaction between a peptide and a single-walled CNT has been shown in experimental studies. [21,22] It has also been shown that the presence of heteroatoms on the aromatic ring have a strong influence on the mode of interaction.…”

“…[21,22] It has also been shown that the presence of heteroatoms on the aromatic ring have a strong influence on the mode of interaction. [23,24] The importance of aromatic content for the interaction between a peptide and a single-walled CNT has been shown in experimental studies. [25] A recent experimental study revealed that p-p stacking interactions between the CNTs and the aromatic residues (Trp, Phe, Tyr) of the proteins were found to play a significant role in determining the strength of the CNT-protein interaction.…”

Structures and energetics of complexation of metal ions with ammonia, water, and benzene: A computational study

“…[6] Kim et al have discussed the interaction of metal ions with biologically and chemically important systems, and studied their role in the active sites of enzymes. [1,[19][20][21][22][23] The studies performed by our group have shown that the strength of cation-p interaction depends on the size of p system, [24,25] the nature of cation [9] the presence of heteroaromatic groups in the p system [26,27] and the presence of solvent and site of solvation. [8] Metal ion interactions with aromatic motifs and their occurrence in proteins have been extensively studied in our group.…”

Energy decomposition analysis of cation–π, metal ion–lone pair, hydrogen bonded, charge‐assisted hydrogen bonded, and π–π interactions

“…DFT–SAPT has emerged as a method of choice to study noncovalent interactions because of its high reliability and efficiency . This theory has been successfully applied to a wide range of noncovalently bound complexes ranging from π–π to cation–π …”

“…[70] DFT-SAPT has emerged as a method of choice to study noncovalent interactions because of its high reliability and efficiency. [71] This theory has been successfully applied to a wide range of noncovalently bound complexes ranging from p-p to cation-p. [72][73][74][75][76][77][78][79][80][81][82] In this study, we have used two most popular EDSs, DFT-SAPT and RVS, to a large number of noncovalently bound complexes. We have used DFT-SAPT, as it is proved to be better for the prediction and interpretation of intermolecular interactions, with accuracy close to that of ab initio coupled cluster theory.…”