Theory Meets Experiment for Noncovalent Complexes: The Puzzling Case of Pnicogen Interactions

Li, Weixing; Spada, Lorenzo; Tasinato, Nicola; Rampino, Sergio; Evangelisti, Luca; Gualandi, Andrea; Cozzi, Pier Giorgio; Melandri, Sonia; Barone, Vincenzo; Puzzarini, Cristina

doi:10.1002/ange.201807751

Cited by 15 publications

(17 citation statements)

References 61 publications

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“…Perhaps even more surprisingly, the directionality of the halogen bond is not a consequence of the electrostatic interaction, but the linear arrangement minimizes the density overlap and drives down the exchange repulsion due to the nonspherical character (polar flattening) of a σ ‐bonded halogen atom . Halogens are not the only atoms to possess a σ ‐hole, and a whole class of other related bonding patterns has been subjected to the SAPT(DFT) (or many‐body SAPT) energy decomposition, including chalcogen, pnicogen, and tetrel bonding …”

Section: The Sapt Formalismmentioning

confidence: 99%

Recent developments in symmetry‐adapted perturbation theory

Patkowski

2019

WIREs Comput Mol Sci

159

144

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Symmetry-adapted perturbation theory (SAPT) is a well-established method to compute accurate intermolecular interaction energies in terms of physical effects such as electrostatics, induction (polarization), dispersion, and exchange. With many theory levels and variants, and several computer implementations available, closed-shell SAPT has been applied to produce numerous intermolecular potential energy surfaces for complexes of experimental interest, and to elucidate the interactions in various complexes relevant to catalysis, organic synthesis, and biochemistry. In contrast, the development of SAPT for general open-shell complexes is still a work in progress. In the last decade, new developments from several research groups, including the author's, have greatly enhanced the capabilities of SAPT. The new and emerging approaches are designed to make SAPT more widely applicable (including interactions involving multireference systems, complexes in arbitrary spin states, and intramolecular noncovalent interactions), more accurate (enhanced description of intramolecular correlation, a better account of exchange effects, relativistic SAPT, and explicitly correlated SAPT), and more efficient (enhanced density-fitted implementations, linearscaling variants, empirical dispersion, and an implementation on graphics processing units).The new developments open up avenues for SAPT applications to an unprecedented variety of weakly interacting complexes.

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Section: The Sapt Formalismmentioning

confidence: 99%

Recent developments in symmetry‐adapted perturbation theory

Patkowski

2019

WIREs Comput Mol Sci

159

144

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“… 1 − 9 The interest is often focused on spectroscopic and structural properties as well as on energetic characterizations, the latter often being coupled with their quantitative interpretation in terms of chemically meaningful concepts (e.g., electrostatics, induction, dispersion, etc.). 2 , 3 , 6 , 7 , 9 …”

Section: Introductionmentioning

confidence: 99%

Unveiling Bifunctional Hydrogen Bonding with the Help of Quantum Chemistry: The Imidazole-Water Adduct as Test Case

2021

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The ubiquitous role of water and its amphiprotic nature call for a deeper insight into the physical–chemical properties of hydrogen-bonded complexes formed with building blocks of biomolecules. In this work, the semiexperimental (SE) approach combined with the template model (TM) protocol allowed the accurate determination of the equilibrium structure of two isomeric forms of the imidazole-water complex. In this procedure, the integration of experiment (thanks to a recent rotational spectroscopy investigation) and theory is exploited, also providing the means of assessing the reliability and accuracy of different quantum-chemical approaches. Overall, this study demonstrated the robustness of the combined SE-TM approach, which can provide accurate results using affordable quantum-chemical methods. Finally, the structural and energetic characteristics of these complexes have been examined in detail and compared with those of analogous heterocycle–water adducts, also exploiting energy decomposition analyses.

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“…Nitrate anions can even act as π‐holes in crystal structures of proteins and small molecules when the negative charge is dampened by interactions such as hydrogen bonding or coordination to a metal . The gas‐phase complex between trimethylamine and nitroethane has been recently elucidated with rotational spectroscopy, revealing that the π‐hole bonding geometry prevails over competing arrangements involving C−H⋅⋅⋅O/N hydrogen bonding …”

Section: Introductionmentioning

confidence: 99%

π‐Hole Interactions Involving Nitro Aromatic Ligands in Protein Structures

Bauzá

Mooibroek

2019

Chemistry A European J

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Studying noncanonical intermolecular interactions between a ligand and a protein constitutes an emerging research field. Identifying synthetically accessible molecular fragments that can engage in intermolecular interactions is a key objective in this area. Here, it is shown that so‐called “π‐hole interactions” are present between the nitro moiety in nitro aromatic ligands and lone pairs within protein structures (water and protein carbonyls and sulfurs). Ample structural evidence was found in a PDB analysis and computations reveal interaction energies of about −5 kcal mol−1 for ligand–protein π‐hole interactions. Several examples are highlighted for which a π‐hole interaction is implicated in the superior binding affinity or inhibition of a nitro aromatic ligand versus a similar non‐nitro analogue. The discovery that π‐hole interactions with nitro aromatics are significant within protein structures parallels the finding that halogen bonds are biologically relevant. This has implications for the interpretation of ligand–protein complexation phenomena, for example, involving the more than 50 approved drugs that contain a nitro aromatic moiety.

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Theory Meets Experiment for Noncovalent Complexes: The Puzzling Case of Pnicogen Interactions

Cited by 15 publications

References 61 publications

Recent developments in symmetry‐adapted perturbation theory

Recent developments in symmetry‐adapted perturbation theory

Unveiling Bifunctional Hydrogen Bonding with the Help of Quantum Chemistry: The Imidazole-Water Adduct as Test Case

π‐Hole Interactions Involving Nitro Aromatic Ligands in Protein Structures

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