Tetrel bonding interaction: an analysis with the block-localized wavefunction (BLW) approach

Wang, Changwei; Aman, Yama; Ji, Xiaoxi; Mo, Yirong

doi:10.1039/c9cp01710k

Cited by 18 publications

(10 citation statements)

References 65 publications

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“…For instance, halogen bonding has been seen to be the combination of charge transfer and electrostatic attraction in a lesser or greater degree, depending, among other factors, on the nature of the atoms and groups involved in the interaction. 4−8 Similar analyses have been carried out on chalcogen, 9−11 pnicogen, 12,13 tetrel, 14,15 or triel bonds. On the other hand, homopolar dihydrogen bonds in alkanes behave differently depending on the substituents attached to the interacting units, going from a pure dispersion-bound system in methane to a considerable charge transfer-stabilized dimer in the case of polyhedranes.…”

Section: ■ Introductionmentioning

confidence: 90%

Understanding the Interplay of Dispersion, Charge Transfer, and Electrostatics in Noncovalent Interactions: The Case of Bromine–Carbonyl Short Contacts

Echeverría

Velásquez

Álvarez

2020

Crystal Growth & Design

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We have performed a combined structural and computational analysis of short contacts between bromine and the carbon atom of a carbonyl group. Surprisingly, 9% of such contacts are arranged in such a way that the positively charged regions of the two atoms involved, i.e., Br and C, are in close contact, so the interaction geometry cannot be predicted in terms of molecular electrostatic potential maps. Remarkably, despite this like-like electrostatic configuration, the interaction energies associated with these contacts are attractive and considerably large (ca. 1 kcal/mol). Comprehensive energy decomposition analysis and natural bond orbital analysis have allowed us to unveil the physical origin of these interactions, which arise from a precise balance between steric factors (Pauli and electrostatics), dispersion, and charge transfer. These results reinforce the idea of noncovalent interactions as a more or less subtle combination of attractive and repulsive forces rather than a “purely electrostatic” or a “purely orbital” process and open the way to explore new types of interactions beyond the electron density holes model.

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Section: ■ Introductionmentioning

confidence: 90%

Understanding the Interplay of Dispersion, Charge Transfer, and Electrostatics in Noncovalent Interactions: The Case of Bromine–Carbonyl Short Contacts

Echeverría

Velásquez

Álvarez

2020

Crystal Growth & Design

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“…Noncovalent interactions in the general form of D···Z–A (D = donor; A = acceptor) are major driving forces in shaping new materials including self-assembling polymers, nanoparticles, and biomolecular assembles. − As such, there is a current and intense interest in the elucidation of the nature of novel noncovalent interactions such as halogen bonding, chalcogen bonding, pnicogen bonding, tetrel bonding, etc. − For many of these interactions, the classical electrostatic interaction, as highlighted with the σ-hole concept, − has been proposed to account for most of the observable trends. A σ-hole can be understood as a region with positive electrostatic potential surrounded by a ring of negative electrostatic potential along the extension of a σ-bond.…”

Section: Introductionmentioning

confidence: 99%

Classical Electrostatic Interaction Is the Origin for Blue-Shifting Halogen Bonds

Wang

2019

Inorg. Chem.

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Studies have shown that, on the one hand, charge transfer (CT) plays a key role in halogen bonds (D•••X−A) (D = donor; X = halogen atom; A = acceptor), suggesting considerable covalent character of halogen bonding. But, on the other hand, it has been proposed that halogen bonding is dominated by the electrostatic attraction between the electropositive σ-hole at the halogen atom X and the electronegative donor D. It has also been wellrecognized that the CT from the donor D to the antibonding σ*(X−A) would weaken and lengthen the X−A bond. Yet, intriguingly, there is a blue-shifting phenomenon in halogen bonding, where the X−A bond contracts with an enhanced stretching vibrational frequency. Here we explored the nature of blueshifting halogen bonds with the iconic case of H 3 N•••ClNO 2 , which exhibits the blue-shifting phenomenon along with a strong CT interaction and its analogous H 3 N•••XNY 2 (X = Cl, Br, and I; Y = O, S). By decomposing the binding energy to a number of energy components and exploring their energy profiles along with the halogen-bonding distances with the block-localized wave function (BLW) method, we showed that the classical electrostatic interaction is the governing factor for the blue-shifting of the X−N bonds. This is further supported by the similar magnitudes of blue-shifting obtained when NH 3 is replaced with atomic point charges in the complexes. Alternatively, by applying external electric field (E-field) along the X−N bond direction, the blue-to-red shifting transition can be identified. This is because both polarization and CT interactions tend to stretch the X−N bond, and both are enhanced simultaneously under the external E-field. Finally, roles of individual energy components are reconfirmed using the force analysis based on the BLW energy decomposition approach.

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“…While the electron-deficient part of the acceptor molecules was concentrated on the π-conjugates of NDI and DNB, respectively (i.e., on the naphthalenediimide and benzene rings). Thus, it was concluded from the electron density pattern (mapped with electrostatic potential) 54 that pyrene-NDI and pyrene-DNB were two potential D−A pairs. Spectroscopic Behaviors of Charge Transfer Interactions.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Tuning Rheological Behaviors of Supramolecular Aqueous Gels via Charge Transfer Interactions

Yang

Shen

et al. 2021

Langmuir

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Rheological properties are critical for determining real applications of supramolecular gels in various fields. Correspondingly, the modulation of gel rheology will be very important for meeting real requirements. In this aspect, a few strategies were applied to tune the rheological behaviors of supramolecular gels, but some specific interactions like charge transfer (CT) interactions were less explored at the molecular level. Herein, we report a pyrene-containing derivative of diphenylalanine as a donor gelator and naphthalenediimide or 3,5dinitrobenzene as matching acceptor molecules. It was found that the viscoelastic properties and strength of the original gel could be tuned through addition of different acceptor molecules to the original gel with changing the ratios of the selected acceptor molecules. As a result, storage modulus was continuously adjusted over a wide range from 190,000 to 50,000 Pa by CT interactions. Furthermore, the mechanism of the CT-induced change in rheological properties was understood and clarified through relevant techniques (e.g., UV−Vis, fluorescence, and FT-IR spectroscopy and TEM). The findings in this work would provide a novel strategy to modulate the rheological properties of supramolecular gels for adaption to broader fields of real applications.

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Tetrel bonding interaction: an analysis with the block-localized wavefunction (BLW) approach

Abstract: In this study, fifty-one iconic tetrel bonding complexes were studied using the block localized wave function (BLW) method which can derive the self-consistent wavefunction for an electron-localized (diabatic) state where charge transfer is strictly deactivated.

Cited by 18 publications

References 65 publications

Understanding the Interplay of Dispersion, Charge Transfer, and Electrostatics in Noncovalent Interactions: The Case of Bromine–Carbonyl Short Contacts

Understanding the Interplay of Dispersion, Charge Transfer, and Electrostatics in Noncovalent Interactions: The Case of Bromine–Carbonyl Short Contacts

Classical Electrostatic Interaction Is the Origin for Blue-Shifting Halogen Bonds

Tuning Rheological Behaviors of Supramolecular Aqueous Gels via Charge Transfer Interactions

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