An insight into intramolecular blue-shifting C H⋯π hydrogen bonds in 1,3-hexadien-5-yne and its halogen-substituted derivatives

Zhang, Lijuan; Li, Dazhi

doi:10.1016/j.chemphys.2018.11.001

Cited by 7 publications

(1 citation statement)

References 55 publications

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“…The relative stability between conformers, depending on the presence or absence of the interaction, is one of the definitions. The electronic energy associated to an isodesmic reaction is another tool for calculating intramolecular interaction energies [ 43 , 44 , 45 , 46 , 47 ] and, in particular, intramolecular hydrogen bonds [ 48 , 49 , 50 , 51 , 52 , 53 ]. An intramolecular interaction may be formally built up by a fictitious chemical reaction and the energy of this reaction is representative of the interaction energy.…”

Section: Computational Detailsmentioning

confidence: 99%

Large Stabilization Effects by Intramolecular Beryllium Bonds in Ortho-Benzene Derivatives

et al. 2021

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Intramolecular interactions are shown to be key for favoring a given structure in systems with a variety of conformers. In ortho-substituted benzene derivatives including a beryllium moiety, beryllium bonds provide very large stabilizations with respect to non-bound conformers and enthalpy differences above one hundred kJ·mol−1 are found in the most favorable cases, especially if the newly formed rings are five or six-membered heterocycles. These values are in general significantly larger than hydrogen bonds in 1,2-dihidroxybenzene. Conformers stabilized by a beryllium bond exhibit the typical features of this non-covalent interaction, such as the presence of a bond critical point according to the topology of the electron density, positive Laplacian values, significant geometrical distortions and strong interaction energies between the donor and acceptor quantified by using the Natural Bond Orbital approach. An isodesmic reaction scheme is used as a tool to measure the strength of the beryllium bond in these systems in terms of isodesmic energies (analogous to binding energies), interaction energies and deformation energies. This approach shows that a huge amount of energy is spent on deforming the donor–acceptor pairs to form the new rings.

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Section: Computational Detailsmentioning

confidence: 99%

Large Stabilization Effects by Intramolecular Beryllium Bonds in Ortho-Benzene Derivatives

et al. 2021

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Sensing mechanism elucidation of a chemosensor based on a metal‐organic framework selective to explosive aromatic compounds

Hidalgo‐Rosa

Treto‐Suárez

Schott

et al. 2020

Int J of Quantum Chemistry

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Theoretical elucidation of the turn-off mechanism of the luminescence of a chemosensor based on a metal-organic framework (MOF) [Zn 2 (OBA) 4 (BYP) 2 ] (BYP: 4,4 0bipyridine; H 2 OBA: 4,4 0-oxybis[benzoic acid]), selective to nitrobenzene (NB) via quantum chemical computations, is presented. The electronic structure and optical properties of Zn-MOF were investigated through the combination of density functional theory (DFT) and time-dependent DFT methods. Our results indicate that the fluorescence emission is governed by a linker (BPY)-to-linker (OBA) charge transfer (LLCT) involving orbitals π-type. Next, the interaction with the analyte was analyzed, where very interesting results were obtained, that is, the lowest unoccupied molecular orbital is now composed of orbitals from NB, which changes the emissive state of the Zn-MOF. This suggests that the LLCT process is blocked, inducing the fluorescence quenching. Otherwise, the Morokuma-Ziegler energy decomposition and natural orbitals for chemical valence on the Zn-MOF-NB interactions were studied in detail, which illustrate the possible channels of charge transfer between Zn-MOF and NB. Finally, we believe that this proposed methodology can be applied to different chemosensor-analyte systems to evidence the molecular and electronic factors that govern the sensing mechanisms.

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A theoretical investigation on the complexes of B3O3H3 with acetylene and its substituted derivatives

Zhang

2019

J Mol Model

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An insight into intramolecular blue-shifting C H⋯π hydrogen bonds in 1,3-hexadien-5-yne and its halogen-substituted derivatives

Cited by 7 publications

References 55 publications

Large Stabilization Effects by Intramolecular Beryllium Bonds in Ortho-Benzene Derivatives

Large Stabilization Effects by Intramolecular Beryllium Bonds in Ortho-Benzene Derivatives

Sensing mechanism elucidation of a chemosensor based on a metal‐organic framework selective to explosive aromatic compounds

A theoretical investigation on the complexes of B3O3H3 with acetylene and its substituted derivatives

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