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Identification of the Tetrel Bonds between Halide Anions and Carbon Atom of Methyl Groups Using Electronic Criterion.

ABSTRACT: The consideration of the disposition of minima of electron density and electrostatic potential along the line between non-covalently bound atoms in systems with Hal^-···CH₃⁻Y (Hal^- = Cl, Br; Y = N, O) fragments allowed to prove that the carbon atom in methyl group serves as an electrophilic site provider. These interactions between halide anion and carbon in methyl group can be categorized as the typical tetrel bonds. Statistics of geometrical parameters for such tetrel bonds in CSD is analyzed. It is established that the binding energy in molecular complexes with tetrel bonds correlate with the potential acting on an electron in molecule (PAEM). The PAEM barriers for tetrel bonds show a similar behavior for both sets of complexes with Br^- and Cl^- electron donors.

SUBMITTER: Bartashevich E

PROVIDER: S-EPMC6471983 | biostudies-literature | 2019 Mar

REPOSITORIES: biostudies-literature

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Identification of the Tetrel Bonds between Halide Anions and Carbon Atom of Methyl Groups Using Electronic Criterion.

Bartashevich Ekaterina E Matveychuk Yury Y Tsirelson Vladimir V

Molecules (Basel, Switzerland) 20190319 6

The consideration of the disposition of minima of electron density and electrostatic potential along the line between non-covalently bound atoms in systems with Hal<sup>-</sup>···CH₃⁻Y (Hal<sup>-</sup> = Cl, Br; Y = N, O) fragments allowed to prove that the carbon atom in methyl group serves as an electrophilic site provider. These interactions between halide anion and carbon in methyl group can be categorized as the typical tetrel bonds. Statistics of geometrical parameters for such tetrel bond ...[more]

PMID: 30893831

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Project description:The structural stability of the extensively studied organic-inorganic hybrid methylammonium tetrel halide perovskite semiconductors, MATtX3 (MA = CH3NH3+; Tt = Ge, Sn, Pb; X = Cl, Br, I), arises as a result of non-covalent interactions between an organic cation (CH3NH3+) and an inorganic anion (TtX3-). However, the basic understanding of the underlying chemical bonding interactions in these systems that link the ionic moieties together in complex configurations is still limited. In this study, ion pair models constituting the organic and inorganic ions were regarded as the repeating units of periodic crystal systems and density functional theory simulations were performed to elucidate the nature of the non-covalent interactions between them. It is demonstrated that not only the charge-assisted N-H···X and C-H···X hydrogen bonds but also the C-N···X pnictogen bonds interact to stabilize the ion pairs and to define their geometries in the gas phase. Similar interactions are also responsible for the formation of crystalline MATtX3 in the low-temperature phase, some of which have been delineated in previous studies. In contrast, the Tt···X tetrel bonding interactions, which are hidden as coordinate bonds in the crystals, play a vital role in holding the inorganic anionic moieties (TtX3-) together. We have demonstrated that each Tt in each [CH3NH3+•TtX3-] ion pair has the capacity to donate three tetrel (σ-hole) bonds to the halides of three nearest neighbor TtX3- units, thus causing the emergence of an infinite array of 3D TtX64- octahedra in the crystalline phase. The TtX44- octahedra are corner-shared to form cage-like inorganic frameworks that host the organic cation, leading to the formation of functional tetrel halide perovskite materials that have outstanding optoelectronic properties in the solid state. We harnessed the results using the quantum theory of atoms in molecules, natural bond orbital, molecular electrostatic surface potential and independent gradient models to validate these conclusions.

Dataset Information

Identification of the Tetrel Bonds between Halide Anions and Carbon Atom of Methyl Groups Using Electronic Criterion.

Publications

Identification of the Tetrel Bonds between Halide Anions and Carbon Atom of Methyl Groups Using Electronic Criterion.

Similar Datasets

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