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Comparison between Tetrel Bonded Complexes Stabilized by ? and ? Hole Interactions.

ABSTRACT: The ?-hole tetrel bonds formed by a tetravalent molecule are compared with those involving a ?-hole above the tetrel atom in a trivalent bonding situation. The former are modeled by TH?, TH?F, and TH?F? (T = Si, Ge, Sn) and the latter by TH?=CH?, THF=CH?, and TF?=CH?, all paired with NH? as Lewis base. The latter ?-bonded complexes are considerably more strongly bound, despite the near equivalence of the ? and ?-hole intensities. The larger binding energies of the ?-dimers are attributed to greater electrostatic attraction and orbital interaction. Each progressive replacement of H by F increases the strength of the tetrel bond, whether ? or ?. The magnitudes of the maxima of the molecular electrostatic potential in the two types of systems are not good indicators of either the interaction energy or even the full Coulombic energy. The geometry of the Lewis acid is significantly distorted by the formation of the dimer, more so in the case of the ?-bonded complexes, and this deformation intensifies the ? and ? holes.

SUBMITTER: Zierkiewicz W

PROVIDER: S-EPMC6100375 | biostudies-literature | 2018 Jun

REPOSITORIES: biostudies-literature

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Comparison between Tetrel Bonded Complexes Stabilized by σ and π Hole Interactions.

Zierkiewicz Wiktor W Michalczyk Mariusz M Scheiner Steve S

Molecules (Basel, Switzerland) 20180611 6

The σ-hole tetrel bonds formed by a tetravalent molecule are compared with those involving a π-hole above the tetrel atom in a trivalent bonding situation. The former are modeled by TH₄, TH₃F, and TH₂F₂ (T = Si, Ge, Sn) and the latter by TH₂=CH₂, THF=CH₂, and TF₂=CH₂, all paired with NH₃ as Lewis base. The latter π-bonded complexes are considerably more strongly bound, despite the near equivalence of the σ and π-hole intensities. The larger binding energies of the π-dimers are attributed to grea ...[more]

PMID: 29891824

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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.

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Comparison between Tetrel Bonded Complexes Stabilized by ? and ? Hole Interactions.

Publications

Comparison between Tetrel Bonded Complexes Stabilized by σ and π Hole Interactions.

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