Tuning Aromaticity of<i>para</i>‐Substituted Benzene Derivatives with an External Electric Field

Dominikowska, Justyna; Palusiak, Marcin

doi:10.1002/cphc.201701203

Cited by 15 publications

(10 citation statements)

References 23 publications

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“…For polar solvents, a change in the values of the dielectric constant has a negligible effect. There are a number of approaches that can be used to properly simulate solvent effects [80][81][82][83][84][85]. None of these approaches are universal and effortlessly applicable to an arbitrary molecular system.…”

Section: Methodsmentioning

confidence: 99%

NMR Properties of the Cyanide Anion, a Quasisymmetric Two-Faced Hydrogen Bonding Acceptor

Shenderovich

Denisov

2021

Symmetry

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The isotopically enriched cyanide anion, (13C≡15N)−, has a great potential as the NMR probe of non-covalent interactions. However, hydrogen cyanide is highly toxic and can decompose explosively. It is therefore desirable to be able to theoretically estimate any valuable results of certain experiments in advance in order to carry out experimental studies only for the most suitable molecular systems. We report the effect of hydrogen bonding on NMR properties of 15N≡13CH···X and 13C≡15NH···X hydrogen bonding complexes in solution, where X = 19F, 15N, and O=31P, calculated at the ωB97XD/def2tzvp and the polarizable continuum model (PCM) approximations. In many cases, the isotropic 13C and 15N chemical shieldings of the cyanide anion are not the most informative NMR properties of such complexes. Instead, the anisotropy of these chemical shieldings and the values of scalar coupling constants, including those across hydrogen bonds, can be used to characterize the geometry of such complexes in solids and solutions. 1J(15N13C) strongly correlates with the length of the N≡C bond.

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Section: Methodsmentioning

confidence: 99%

NMR Properties of the Cyanide Anion, a Quasisymmetric Two-Faced Hydrogen Bonding Acceptor

Shenderovich

Denisov

2021

Symmetry

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“…A series of papers was devoted to atomic polarizabilities, that is polarization of the atomic charge distribution in molecules [1][2][3][4][5]. Among other effects, one can mention the tuning of aromaticity of para substituted benzene derivatives [6] and polycalicenes [7] imposed by the field. The most interesting result for us in the first paper was finding the dipole moment direction reversal in paminophenol, p-nitrobenzonitrile, and p-nitrophenol at a sufficiently high field strength and at its proper direction toward the main molecular axes.…”

Section: Introductionmentioning

confidence: 99%

The response of electronic and energetic properties of conjugated vs aromatic molecules to an external uniform electric field

Sadlej-Sosnowska

2019

Struct Chem

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The susceptibility of electric and energetic properties of two sets of molecules to perturbation in a uniform electric field was investigated. The molecules of one set were deca-1,3,5,7-pentaene terminated with two functional groups, R 1 and R 2 ; those of the second set were 4-R 1-4′-R 2-p-diphenylbenzenes, with R 1 and R 2 being the same as in the polyene set. The polyene and aromatic molecules had similar lengths of the system of conjugated bonds between the two most extreme carbon atoms. Dipole moments were used as determinants of the overall charge transfer within the molecules. The electric field was directed along the main (longest) axes of the molecules from the negative pole to the positive. Comparison of the effect of the charge relocation in both sets of conjugated molecules revealed that the charge transfer imposed by the electric field was more efficient in the polyenes than in the aromatic compounds; however, for the molecule pairs with the same R 1 and R 2 , reversal of the dipole moment direction falls at the same field strength. Parabolic dependence of the molecules' energy as a function of field strength can also be interpreted in terms of the response of electron density to an electric field.

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“…However, it can be successfully accounted for by the adduct under field approach (AuF) [37]. The dependence of the electron density on the applied electric field and the associated changes in chemical and spectral properties were widely studied [38][39][40][41][42][43]. Within the AuF approach, both the structure and NMR properties were calculated in the presence of an external electric field.…”

Section: Calculation Of Nmr Chemical Shiftsmentioning

confidence: 99%

Solid State NMR for Nonexperts: An Overview of Simple but General Practical Methods

Shenderovich

Limbach

2021

Solids

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There are varieties of methods available for the exploration of solids using nuclear magnetic resonance (NMR) spectroscopy. Some of these methods are quite sophisticated, others require specialized equipment. This review is addressed to those for whom NMR is not the main research method. It discusses simple methods that can be applied to solids with little or no adaptation to a specific system. Despite their technical simplicity and ease of use, these methods are powerful analytical tools that provide unique insights into the structure, dynamics, and noncovalent interactions in homo- and heterogeneous systems. Particular attention is paid to the characterization of porous materials and solids containing phosphorus. 31P NMR of organometallic compounds has been used as an example of how theoretical calculations can help in deeper analysis of experimental data.

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Tuning Aromaticity ofpara‐Substituted Benzene Derivatives with an External Electric Field

Cited by 15 publications

References 23 publications

NMR Properties of the Cyanide Anion, a Quasisymmetric Two-Faced Hydrogen Bonding Acceptor

NMR Properties of the Cyanide Anion, a Quasisymmetric Two-Faced Hydrogen Bonding Acceptor

The response of electronic and energetic properties of conjugated vs aromatic molecules to an external uniform electric field

Solid State NMR for Nonexperts: An Overview of Simple but General Practical Methods

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