Molecular Electrostatic Potentials: Significance and Applications

Politzer, Peter; Murray, Jane S.

doi:10.1002/9781119683353.ch7

Cited by 28 publications

(20 citation statements)

References 122 publications

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“…Clearly, the nucleophilic portions of a given entity interact attractively with the regions of the most positive electrostatic potential on a neighboring (or the same) entity, leading to σ•••lone-pair, σ•••π, σ•••σ and π•••π interactions. This is the case for interactions that are coulombic in origin (a positive site attracting a negative one [54, 80,95]). However, there are examples known in which anti-electrostatic interactions have been shown to occur [96,97], as well as instances where a positive site attracts a positive site [98], and a negative site attracts a negative site [51] when they are in close proximity.…”

Section: Computational Detailsmentioning

confidence: 99%

“…This bonding has been referred to as a "close contact", or simply "a non-covalent interaction" [75]. The criterion, however, rejects those interactions that have intermolecular bond distances slightly larger than the sum of vdW radii of Pn and D. This could be misleading because the proposed vdW radii [76,77] are not necessarily accurate [78] (within an uncertainty of ±0.2 Å) because a spherical symmetry of atoms in molecules was generally assumed for their determination [75], and that there have been many systems reported theoretically and experimentally that fail to strictly obey the criterion [79][80][81][82][83]. Since the charge density profile of atoms in molecules is anisotropic, the vdW "radius" of an atom in a molecular entity is likely to vary between molecular entities.…”

Section: Introductionmentioning

confidence: 99%

“…While doing so, directional features, together with chemical intuition and interpretations provided by the original authors, were considered. In addition, the underlying concepts of molecular electrostatic surface potentials (MESP) [79][80][81][82][83] were utilized in several instances to verify the putative interactions that emerged from the "less than the sum of the vdW radii" concept.…”

Section: Introductionmentioning

confidence: 99%

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The Nitrogen Bond, or the Nitrogen-Centered Pnictogen Bond: The Covalently Bound Nitrogen Atom in Molecular Entities and Crystals as a Pnictogen Bond Donor

Varadwaj

Marques

et al. 2022

Compounds

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The nitrogen bond in chemical systems occurs when there is evidence of a net attractive interaction between the electrophilic region associated with a covalently or coordinately bound nitrogen atom in a molecular entity and a nucleophile in another, or the same molecular entity. It is the first member of the family of pnictogen bonds formed by the first atom of the pnictogen family, Group 15, of the periodic table, and is an inter- or intra-molecular non-covalent interaction. In this featured review, we present several illustrative crystal structures deposited in the Cambridge Structure Database (CSD) and the Inorganic Crystal Structure Databases (ICSD) to demonstrate that imide nitrogen is not the only instance where nitrogen can act as an electrophilic agent. Analysis of a set of carefully chosen illustrative crystal systems shows that a covalently bound nitrogen atom in a variety of molecular entities features a σ-hole or even a π-hole, and these have the ability to sustain attractive engagements with negative sites to form inter- and/or intramolecular interactions that drive, or assist, the formation of a crystalline phase.

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Section: Computational Detailsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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The Nitrogen Bond, or the Nitrogen-Centered Pnictogen Bond: The Covalently Bound Nitrogen Atom in Molecular Entities and Crystals as a Pnictogen Bond Donor

Varadwaj

Marques

et al. 2022

Compounds

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“…The generated molecular electrostatic potential in the space around a molecule, including the charge distribution, is very helpful in understanding the sites for electrophilic attacks and nucleophilic reactions. Also, exploring the charge distribution around the molecule is essential for studying biological recognition processes and hydrogen bonding interactions [42][43][44][45]. Hence, the molecular electrostatic potentials for complexes 2 and 5 were calculated from the optimized geometry (Fig.…”

Section: Molecular Electrostatic Potentialmentioning

confidence: 99%

Synthesis, DFT Calculations, DNA Interaction, and Antimicrobial Studies of Some Mixed Ligand Complexes of Oxalic Acid and Schiff Base Trimethoprim with Various Metal Ions

Abdalrazaq

Jbarah²,

Al‐Noor³

et al. 2022

Indones. J. Chem.

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Mixed ligand metal complexes are synthesized from oxalic acid with Schiff base, and the Schiff base was obtained from trimethoprim and acetylacetone. The synthesized complexes were of the type [M(L1)(L2)], where the metal, M, is Ni(II), Cu(II), Cr(III), and Zn(II), L1 corresponds to the trimethoprim ((Z)-4-((4-amino-5-(3,4,5-trimethoxybenzyl)pyrimidine-2-yl)imino)pentane-2-one) as the first ligand and L2 represent the oxalate anion ( ) as a second ligand. Characterization of the prepared compounds was performed by elemental analysis, molar conductivity, magnetic measurements, 1H-NMR, 13C-NMR, FT-IR, and Ultraviolet-visible (UV-Vis) spectral studies. The recorded infrared data is reinforced with density functional theory (DFT) calculations. Also, the recorded and calculated IR spectra of the complexes suggested that the coordination of Schiff base is a bidentate ligand with Cu and Ni complexes and a tridentate ligand with Co, Cr, and Zn complexes. The electronic structures of the complexes were investigated by DFT calculations, showing several degrees of HOMO-LUMO energy gaps between complexes. The complexes were studied for their DNA interaction activities. The synthesized ligand and its metal complexes were evaluated for antimicrobial properties against bacterial strains of Bacillus subtilis (G+), Enterobacter cloacae (G-), and Staphylococcus aureus (G+). These complexes considered in this study showed good antimicrobial activity.

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“…46 The MESP calculated from ab initio wave functions were used to interpret the protonation of formamide, to assess the difference in reactivity of some sites towards electrophilic reagents for five-membered heterocycles, and to compare different protonation sites in the nucleic acid bases such as adenine, thymine, and cytosine. 45,[47][48][49][50] Numerous MESP-based studies carried out by Politzer and Murray have contributed largely towards establishing MESP as a fundamental quantity 10,51 for the theoretical analysis of chemical reactivity, [51][52][53][54][55][56][57][58][59][60][61][62][63][64][65][66][67] such as analysis of nucleophilicity, crystal density, explosive nature of compounds, [68][69][70] noncovalent intermolecular interactions, etc. 71 Politzer et al proposed the σ-hole interaction theory to describe noncovalent bonding scenarios arising from group 14 (tetrels), 15 (pnicogens), 16 (chalcogens), and 17 (halogens) elements.…”

mentioning

confidence: 99%

Molecular electrostatic potential analysis: A powerful tool to interpret and predict chemical reactivity

Suresh

Remya

Anjalikrishna

2022

WIREs Comput Mol Sci

152

108

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The molecular electrostatic potential (MESP) V(r) data derived from a reliable quantum chemical method has been widely used for the interpretation and prediction of various aspects of chemical reactivity. A rigorous mapping of the MESP topology is achieved by computing both rV(r) data and the elements of the Hessian matrix at the critical points where rV(r) = 0. In the MESP topology, intra-and inter-molecular bonded regions show the characteristic (3, À1) bond critical points (BCPs) while the electron-rich regions such as lone pair and π-bonds show (3, +3) minimum (V min ) CPs. The V min analysis provides a simple and powerful technique to characterize the electron-rich region in a molecular system as it corresponds to the condensed information of the wave function at this point due to the nuclei and electronic distribution through the Coulomb's law. The V min analysis has been successfully applied to explain the phenomena related to chemical reactivity such as π-conjugation, aromaticity, substituent effect, ligand electronic effects, trans-influence, redox potential, activation energy, cooperativity, noncovalent interactions, and so on. The MESP parameters ΔV min and ΔV n , derived for arene systems have been used as powerful measures of substituent effects while V min at the lone pair region of ligands has been used as a reliable electronic parameter to assess their σ-donating ability to metal centers. Furthermore, strong predictions on the intermolecular interactive behavior of molecular systems can be made from MESP topology studies. This review summarizes the chemical reactivity applications offered by MESP topology analysis for a large variety of organic, organometallic, and inorganic molecular systems.

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Molecular Electrostatic Potentials: Significance and Applications

Cited by 28 publications

References 122 publications

The Nitrogen Bond, or the Nitrogen-Centered Pnictogen Bond: The Covalently Bound Nitrogen Atom in Molecular Entities and Crystals as a Pnictogen Bond Donor

The Nitrogen Bond, or the Nitrogen-Centered Pnictogen Bond: The Covalently Bound Nitrogen Atom in Molecular Entities and Crystals as a Pnictogen Bond Donor

Synthesis, DFT Calculations, DNA Interaction, and Antimicrobial Studies of Some Mixed Ligand Complexes of Oxalic Acid and Schiff Base Trimethoprim with Various Metal Ions

Molecular electrostatic potential analysis: A powerful tool to interpret and predict chemical reactivity

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