Anion-π Interactions in Supramolecular Chemistry and Catalysis

Bauzá, Antonio; Deyà, Pere M.; Frontera, Antonio

doi:10.1007/978-3-319-14163-3_16

Cited by 14 publications

(9 citation statements)

References 115 publications

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“…A theoretical study of the possible interaction of the π-cloud of C 6 F 6 with several small electron donor molecules (HF, HLi, CH 2 , NCH, and CNH), as well as many others, has been reported [43]. Similar studies, including anionic complexes of C 6 F 6 , have also appeared elsewhere [44][45][46][47][48], with the MP2 level binding energy for the C 6 F 6 ···X − (X = F, Cl, Br) anionic complexes varying between −12.19 and −18.63 kcal mol −1 [49].…”

Section: Of 34mentioning

confidence: 80%

Can Combined Electrostatic and Polarization Effects Alone Explain the F···F Negative-Negative Bonding in Simple Fluoro-Substituted Benzene Derivatives? A First-Principles Perspective

Varadwaj

Marques

et al. 2018

Computation

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The divergence of fluorine-based systems and significance of their nascent non-covalent chemistry in molecular assemblies are presented in a brief review of the field. Emphasis has been placed to show that type-I and -II halogen-centered F···F long-ranged intermolecular distances viable between the entirely negative fluorine atoms in some fluoro-substituted dimers of C 6 H 6 can be regarded as the consequence of significant non-covalent attractive interactions. Such attractive interactions observed in the solid-state structures of C 6 F 6 and other similar fluorine-substituted aromatic compounds have frequently been underappreciated. While these are often ascribed to crystal packing effects, we show using first-principles level calculations that these are much more fundamental in nature. The stability and reliability of these interactions are supported by their negative binding energies that emerge from a supermolecular procedure using MP2 (second-order Møller-Plesset perturbation theory), and from the Symmetry Adapted Perturbation Theory, in which the latter does not determine the interaction energy by computing the total energy of the monomers or dimer. Quantum Theory of Atoms in Molecules and Reduced Density Gradient Non-Covalent Index charge-density-based approaches confirm the F···F contacts are a consequence of attraction by their unified bond path (and bond critical point) and isosurface charge density topologies, respectively. These interactions can be explained neither by the so-called molecular electrostatic surface potential (MESP) model approach that often demonstrates attraction between sites of opposite electrostatic surface potential by means of Coulomb's law of electrostatics, nor purely by the effect of electrostatic polarization. We provide evidence against the standalone use of this approach and the overlooking of other approaches, as the former does not allow for the calculation of the electrostatic potential on the surfaces of the overlapping atoms on the monomers as in the equilibrium geometry of a complex. This study thus provides unequivocal evidence of the limitation of the MESP approach for its use in gaining insight into the nature of reactivity of overlapped interacting atoms and the intermolecular interactions involved.

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Section: Of 34mentioning

confidence: 80%

Can Combined Electrostatic and Polarization Effects Alone Explain the F···F Negative-Negative Bonding in Simple Fluoro-Substituted Benzene Derivatives? A First-Principles Perspective

Varadwaj

Marques

et al. 2018

Computation

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“…1c belongs formally to a subclass of lp-p interactions named anion-p interactions. 4,[9][10][11][12][13][14][15][16][17] Anion-p interactions were theoretically predicted to attract anions such as Cl À or Br À toward the center of substituted/heterocyclic aromatic systems. [18][19][20] Subsequent experimental and theoretical work 8,10 revealed that in many cases, anions would bind to substituted aromatic systems in a different, ''off-center'' mode, reminiscent of that seen in Jackson-Meisenheimer s-complexes.…”

Section: Introductionmentioning

confidence: 99%

“…10,12 Some confusion has arisen from the fact that many authors understand that under anion-p interactions the first group can be exclusively found and argue that anion-p interactions are noncovalent interactions, driven by electrostatic, polarization, and dispersion forces (ref. 4,17,22,23…”

Section: Introductionmentioning

confidence: 99%

Lone-pair–π interactions: analysis of the physical origin and biological implications

Novotný

Bazzi

Marek

et al. 2016

Phys. Chem. Chem. Phys.

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Lone-pair-π (lp-π) interactions have been suggested to stabilize DNA and protein structures, and to participate in the formation of DNA-protein complexes. To elucidate their physical origin, we have carried out a theoretical multi-approach analysis of two biologically relevant model systems, water-indole and water-uracil complexes, which we compared with the structurally similar chloride-tetracyanobenzene (TCB) complex previously shown to contain a strong charge-transfer (CT) binding component. We demonstrate that the CT component in lp-π interactions between water and indole/uracil is significantly smaller than that stabilizing the Cl(-)-TCB reference system. The strong lp(Cl(-))-π(TCB) orbital interaction is characterized by a small energy gap and an efficient lp-π* overlap. In contrast, in lp-π interactions between water and indole or uracil, the corresponding energy gap is larger and the overlap less efficient. As a result, water-uracil and water-indole interactions are weak forces composed by smaller contributions from all energy components: electrostatics, polarization, dispersion, and charge transfer. In addition, indole exhibits a negative electrostatic potential at its π-face, making lp-π interactions less favorable than O-Hπ hydrogen bonding. Consequently, some of the water-tryptophan contacts observed in X-ray structures of proteins and previously interpreted as lp-π interactions [Luisi, et al., Proteins, 2004, 57, 1-8], might in fact arise from O-Hπ hydrogen bonding.

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“…On the other hand, hydrogen bonding is probably the most studied noncovalent interaction. 118,119 Several other stabilizing non-covalent interactions with potential chemical and biological applications have also been studied, including halogen bonding [216][217][218][219] , pnicogen bonding [220][221][222] , and anionic [120][121][122][123] interactions. Therefore, we designed our training set to contain representative candidates from the interaction types mentioned above.…”

Section: Training and Validation Data Setsmentioning

confidence: 99%

Fast and accurate quantum mechanical modeling of large molecular systems using small basis set Hartree–Fock methods corrected with atom-centered potentials

Prasad

Otero-de-la-Roza

DiLabio

2022

Preprint

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There has been significant interest in developing fast and accurate quantum mechanical methods for modeling large molecular systems. In this work, by utilizing a machine-learning regression technique, we have developed new low-cost quantum mechanical approaches to model large molecular systems. The developed approaches rely on using one-electron Gaussian-type functions called atom-centered potentials (ACPs) to correct for the basis set incompleteness and the lack of correlation effects in the underlying minimal or small basis set Hartree-Fock (HF) methods. In particular, ACPs are proposed for ten elements common in organic and bio-organic chemistry (H, B, C, N, O, F, Si, P, S, and Cl) and four different base methods: two minimal basis sets (MINIs and MINIX) plus a double-ζ basis set (6-31G*) in combination with dispersion-corrected HF (HF-D3/MINIs, HF-D3/MINIX, HF-D3/6-31G*), and the HF-3c method. The new ACPs are trained on a very large set (73832 data points) of non-covalent properties (interaction and conformational energies) and validated additionally on a set of 32048 data points. All reference data is of complete basis set coupled-cluster quality, mostly CCSD(T)/CBS. The proposed ACP-corrected methods are shown to give errors in the tenths of a kcal/mol range for non-covalent interaction energies and up to 2 kcal/mol for molecular conformational energies. More importantly, the average errors are similar in the training and validation sets, confirming the robustness and applicability of these methods outside the boundaries of the training set. In addition, the performance of the new ACP-corrected methods is similar to complete basis set DFT but at a cost that is orders of magnitude lower, and the proposed ACPs can be used in any computational chemistry program that supports effective-core potentials without modification. It is also shown that ACPs improve the description of covalent and non-covalent bond geometries of the underlying methods and that the improvement brought about by the application of the ACPs is directly related to the number of atoms to which they are applied, allowing the treatment of systems containing some atoms for which ACPs are not available. Overall, the ACP-corrected methods proposed in this work constitute an alternative accurate, economical, and reliable quantum mechanical approach to describe the geometries, interaction energies, and conformational energies of systems with hundreds to thousands of atoms.

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Anion-π Interactions in Supramolecular Chemistry and Catalysis

Cited by 14 publications

References 115 publications

Can Combined Electrostatic and Polarization Effects Alone Explain the F···F Negative-Negative Bonding in Simple Fluoro-Substituted Benzene Derivatives? A First-Principles Perspective

Can Combined Electrostatic and Polarization Effects Alone Explain the F···F Negative-Negative Bonding in Simple Fluoro-Substituted Benzene Derivatives? A First-Principles Perspective

Lone-pair–π interactions: analysis of the physical origin and biological implications

Fast and accurate quantum mechanical modeling of large molecular systems using small basis set Hartree–Fock methods corrected with atom-centered potentials

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