Tuning the Electronic Properties of the Dative N−B Bond with Associated O−B Interaction: Electron Localizability Indicator from X‐Ray Wavefunction Refinement

Chęcińska, Lilianna; Mebs, Stefan; Ośmiałowski, Borys; Zakrzewska, Anna; Ejsmont, Krzysztof; Kohout, Miroslav

doi:10.1002/cphc.201600223

Cited by 11 publications

(9 citation statements)

References 62 publications

(80 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The derived B–N bond QTAIM properties (see Table ) can also be confronted with the ones already reported in the literature. Both in our previous work, and in the works by Mebs et al , and Chęcińska et al, the experimentally derived electron density values are very much comparable to the results determined in the current study, and they range from 0.76 to 1.08 e·Å –3 . More peculiar behavior is observed for the Laplacian.…”

Section: Results and Discussionsupporting

confidence: 91%

“…In our previous work, devoted to a model arylboronic azaester crystal, the determined Laplacian was equal to −4.36(8) e·Å –5 , which has an opposite sign to the one determined in this contribution. On the other hand, in the majority of studies, as reported by other groups, − the Laplacian exhibits a positive sign. This can be explained by the change of the B–N interaction character across many complexes and bonding distances, as described by us in details .…”

Section: Results and Discussionmentioning

confidence: 83%

See 1 more Smart Citation

Ground-State Charge-Density Distribution in a Crystal of the Luminescent ortho-Phenylenediboronic Acid Complex with 8-Hydroxyquinoline

et al. 2018

View full text Add to dashboard Cite

This contribution is devoted to the first electron density studies of a luminescent oxyquinolinato boron complex in the solid state. ortho-Phenylenediboronic acid mixed with 8-hydroxyquinoline in dioxane forms high-quality single crystals via slow solvent evaporation, which allows successful high resolution data collection (sin θ/λ = 1.2 Å) and charge density distribution modeling. Particular attention has been paid to the boron-oxygen fragment connecting the two parts of the complex, and to the solvent species exhibiting anharmonic thermal motion. The experiment and theory compared rather well in terms of atomic charges and volumes, except for the boron centers. Boron atoms, as expected, constitute the most electron-deficient species in the complex molecule, whereas the neighboring oxygen and carbon atoms are the most significantly negatively charged ones. This part of the molecule appears to be very much involved in the charge transfer occurring between the acid fragment and oxyquinoline moiety leading to the observed fluorescence, as supported by the time-dependent density functional theory (TDDFT) results and the generated transition density maps. TDDFT calculations indicated that p-type atomic orbitals contributing to the HOMO-1, HOMO, and LUMO play the major role in the lowest energy transitions, and enabled further comparison with the charge density features, which is discussed in details. Furthermore, the results confirmed the known fact the Q ligand character is most important for the spectroscopic properties of this class of complexes.

show abstract

Section: Results and Discussionsupporting

confidence: 91%

Section: Results and Discussionmentioning

confidence: 83%

Ground-State Charge-Density Distribution in a Crystal of the Luminescent ortho-Phenylenediboronic Acid Complex with 8-Hydroxyquinoline

et al. 2018

View full text Add to dashboard Cite

show abstract

“…Working in this sense, Kohout have proposed the Electron Localizability Indicator (ELI–D) [14,15] which is based on the motion of same spin electron density. ELI–D is an useful tool for the detection of chemical bonding signatures in molecule or crystal [16,17] . The combination of AIM and ELI–D approaches is also an issue to determine the Raub‐Jansen Index (RJI) [18,19] which is an appropriate tool to describe the bond polarity.…”

Section: Introductionmentioning

confidence: 99%

Exploring The Sequence of Electron Density Along The Chemical Reactions Between Carbonyl Oxides And Ammonia/Water Using Bond Evolution Theory

et al. 2021

View full text Add to dashboard Cite

The molecular mechanism of the reactions between four carbonyl oxides and ammonia/water are investigated using the M06‐2X functional together with 6‐311++G(d,p) basis set. The analysis of activation and reaction enthalpy shows that the exothermicity of each process increased with the substitution of electron donating substituents (methyl and ethenyl). Along each reaction pathway, two new chemical bonds C−N/C−O and O−H are expected to form. A detailed analysis of the flow of the electron density during their formation have been characterized from the perspective of bonding evolution theory (BET). For all reaction pathways, BET revealed that the process of C−N and O−H bond formation takes place within four structural stability domains (SSD), which can be summarized as follows: the depopulation of V(N) basin with the formation of first C−N bond (appearance of V(C,N) basin), cleavage of N−H bond with the creation of V(N) and V(H) monosynaptic basin, and finally the V(H,O) disynaptic basin related to O−H bond. On the other hand, in the case of water, the cleavage of O−H bond with the formation of V(O) and V(H) basins is the first stage, followed by the formation of the O−H bond as a second stage, and finally the creation of C−O bond.

show abstract

“…X-ray restrained wavefunctions have been used in diverse studies for the analysis of crystal interactions and properties, e.g. 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] .…”

Section: Introductionmentioning

confidence: 99%

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

Ernst

Genoni

Macchi

2020

Journal of Molecular Structure

View full text Add to dashboard Cite

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.

show abstract

Tuning the Electronic Properties of the Dative N−B Bond with Associated O−B Interaction: Electron Localizability Indicator from X‐Ray Wavefunction Refinement

Cited by 11 publications

References 62 publications

Ground-State Charge-Density Distribution in a Crystal of the Luminescent ortho-Phenylenediboronic Acid Complex with 8-Hydroxyquinoline

Ground-State Charge-Density Distribution in a Crystal of the Luminescent ortho-Phenylenediboronic Acid Complex with 8-Hydroxyquinoline

Exploring The Sequence of Electron Density Along The Chemical Reactions Between Carbonyl Oxides And Ammonia/Water Using Bond Evolution Theory

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

Contact Info

Product

Resources

About