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

Literature Information

Publication Date 2012-08-10
DOI 10.1039/C2CP41834G
Impact Factor 3.676
Authors

Bhaskar Sharma, Deivasigamani Umadevi, G. Narahari Sastry


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Abstract

High level ab initio and hybrid DFT methods have been employed to investigate the interactions of metal ions (Li+ and Mg2+) with N and P substituted six membered heteroaromatics (CH)6−m−nNmPn. 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.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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