Complementary bonding analysis of the N–Si interaction in pentacoordinated silicon compounds using quantum crystallography

Fugel, Malte; Ponomarenko, Maxim V.; Hesse, Maxie F.; Malaspina, Lorraine A.; Kleemiss, Florian; Sugimoto, Kunihisa; Genoni, Alessandro; Röschenthaler, Gerd‐Volker; Grabowsky, Simon

doi:10.1039/c9dt02772f

Cited by 8 publications

(3 citation statements)

References 66 publications

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“…for refractive indices [19,20] or for the study of bonds [21][22][23][24][25] , etc. While the majority of XRW studies focused on the electron density and its related properties in crystals, the XRW technique also provides molecular orbitals that were successfully used, for example, in the study of hypervalency [26][27][28] . These investigations on hypervalency showed that the use of both, electron density and molecular orbitals (as we have done in this study), allows for a full exploitation of the X-ray restrained wavefunction technique.…”

Section: Introductionmentioning

confidence: 99%

Analysis of crystal field effects and interactions using X-ray restrained ELMOs

Ernst

Genoni

Macchi

2020

Journal of Molecular Structure

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The purpose of this study is to assess the capability of X-ray restrained molecular wavefunction methods to reproduce the perturbation due to the crystal field. The effect of the crystal environment on the molecular charge densities has been thoroughly investigated experimentally and theoretically. However, the same analysis in terms of molecular orbitals is unprecedented. We specifically analysed the extremely localized molecular orbitals (ELMOs) because they allow for a valence bond like interpretation that is closer to the typical chemical reasoning. For a set of test molecules, we calculated first principles wavefunctions (called primary wavefunctions) and the corresponding scattered intensities (primary structure factors), that we afterwards used for X-ray restrained Hartree-Fock and ELMO calculations. This mimics the typical procedure of modelling wavefunctions from experimental X-ray diffraction, having the primary wavefunction as benchmark. This study follows a previous investigation concerning the effects of electron correlation, where it was shown that those subtle features could be retrieved only to a minor extent. The electric field generated by surrounding molecules is instead more substantial. Therefore, retrieving this information should be more successful and, in case, extremely useful for supramolecular chemistry and crystal engineering. The work also provides useful indications to experimentalists who want to exploit the potentialities offered by the X-ray restrained wavefunction methods.

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Section: Introductionmentioning

confidence: 99%

Analysis of crystal field effects and interactions using X-ray restrained ELMOs

Ernst

Genoni

Macchi

2020

Journal of Molecular Structure

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“…In some previous studies that used XCW fitting, results were based on hydrogen atom ADPs freely refined in a preceding HAR under the assumption that this procedure is superior to XCW fitting with isotropic hydrogen displacement parameters. [68][69][70] In these studies, the hydrogen atom ADPs appeared to be physically reasonable, but the underlying assumption was, to the best of our knowledge, never tested. Here, we compare the residual densities between XCW_aniso and XCW_iso models for Mg and 8HQ HM that bear both physically reasonable and unreasonable hydrogen atom ADPs.…”

Section: Xcw Fittingmentioning

confidence: 95%

Hydrogen atoms in bridging positions from quantum crystallographic refinements: influence of hydrogen atom displacement parameters on geometry and electron density

et al. 2020

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“…[36] These quantumchemical tools employ schemes for partitioning the multidimensional wavefunction and the total electron density into localised regions, as well as for decomposing the total interaction energy into physically meaningful components. Nowadays, these approaches are commonplace in studies on chemical stability and reactivity, [37][38][39][40][41][42] catalysis, [43][44][45] biomolecular interactions, [46,47] molecular crystals, [48][49][50] and organic electronics. [51][52][53] The purpose of this work is twofold: on the one hand, we demonstrate that these approaches can be applied to MOFs and provide meaningful insight into the host-guest interactions.…”

Section: Introductionmentioning

confidence: 99%

Strength and Nature of Host‐Guest Interactions in Metal‐Organic Frameworks from a Quantum‐Chemical Perspective

Ernst

Gryn’ova

2022

ChemPhysChem

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Metal-organic frameworks (MOFs) offer a convenient means for capturing, transporting, and releasing small molecules. Their rational design requires an in-depth understanding of the underlying non-covalent host-guest interactions, and the ability to easily and rapidly pre-screen candidate architectures in silico.In this work, we devised a recipe for computing the strength and analysing the nature of the host-guest interactions in MOFs. By assessing a range of density functional theory methods across periodic and finite supramolecular cluster scale we find that appropriately constructed clusters readily reproduce the key interactions occurring in periodic models at a fraction of the computational cost. Host-guest interaction energies can be reliably computed with dispersion-corrected density functional theory methods; however, decoding their precise nature demands insights from energy decomposition schemes and quantum-chemical tools for bonding analysis such as the quantum theory of atoms in molecules, the non-covalent interactions index or the density overlap regions indicator.

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Complementary bonding analysis of the N–Si interaction in pentacoordinated silicon compounds using quantum crystallography

Abstract: The unique combination of quantum crystallography and complementary bonding analysis is used to investigate the bonding of pentacoordinated silicon atoms.

Cited by 8 publications

References 66 publications

Analysis of crystal field effects and interactions using X-ray restrained ELMOs

Analysis of crystal field effects and interactions using X-ray restrained ELMOs

Hydrogen atoms in bridging positions from quantum crystallographic refinements: influence of hydrogen atom displacement parameters on geometry and electron density

Strength and Nature of Host‐Guest Interactions in Metal‐Organic Frameworks from a Quantum‐Chemical Perspective

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