On the nature of inter- and intramolecular interactions involving benzo[h]quinoline and 10-hydroxybenzo[h]quinoline: Electronic ground state vs excited state study

Jezierska, Aneta; Kizior, Beata; Szyja, Bartłomiej M.; Panek, Jarosław J.

doi:10.1016/j.molstruc.2021.130126

Cited by 7 publications

(6 citation statements)

References 60 publications

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“…This implies that the EDPT is not thermodynamically favored, and this mechanism should not be considered to be plausible. These values, however, do not match exactly the 3.4 eV value calculated using TD-DFT method in our previous study [30]. This discrepancy can be a result of many factors.…”

Section: Constrained Density Functional Theory (Cdft) Electronic Structure Analysis Of Benzo[h]quinoline-2-methylresorcinol Dimer and Tricontrasting

confidence: 87%

“…As far as the complexes with 2-methylresorcinol are concerned, we defined the donor and acceptor boundary along the intermolecular H-bond between the 2-methylresorcinol and benzo[h]quinoline. The charge transfer between the molecules forming the complex was identified in our previous work [30] to be caused by the electronic excitation. The relaxation of the complex was determined to be the radiationless one, occurring via the conical intersection of S0 and S1 states.…”

Section: Constrained Density Functional Theory (Cdft) Electronic Structure Analysis Of Benzo[h]quinoline-2-methylresorcinol Dimer and Trimentioning

confidence: 90%

“…An initial insight into the behavior of HBQ as well as benzo[h]quinoline-2-methylresorcinol complex, with emphasis on the molecular forces governing the behavior of these two systems, was carried out based on the DFT static models [30]. The most important findings of this study amounted to the following facts: the influence of the polar environment (crystal field) on aromaticity was rather minor; while the spontaneous proton transfer was not preferable in the electronic ground state of both HBQ and benzo[h]quinoline-2-methylresorcinol complex, it was possible in the excited state as modelled by the TD-DFT approach; and finally-most important from the point of view of intermolecular non-covalent interactions-the Symmetry-Adapted Perturbation Theory (SAPT) analysis showed the O-H...N intermolecular hydrogen bond of the benzo[h]quinoline-2-methylresorcinol complex to be only ca.…”

Section: Introductionmentioning

confidence: 99%

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Sensitivity of Intra- and Intermolecular Interactions of Benzo[h]quinoline from Car–Parrinello Molecular Dynamics and Electronic Structure Inspection

Panek

Zasada

Szyja

et al. 2021

IJMS

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The O-H...N and O-H...O hydrogen bonds were investigated in 10-hydroxybenzo[h]quinoline (HBQ) and benzo[h]quinoline-2-methylresorcinol complex in vacuo, solvent and crystalline phases. The chosen systems contain analogous donor and acceptor moieties but differently coupled (intra- versus intermolecularly). Car–Parrinello molecular dynamics (CPMD) was employed to shed light onto principle components of interactions responsible for the self-assembly. It was applied to study the dynamics of the hydrogen bonds and vibrational features as well as to provide initial geometries for incorporation of quantum effects and electronic structure studies. The vibrational features were revealed using Fourier transformation of the autocorrelation function of atomic velocity and by inclusion of nuclear quantum effects on the O-H stretching solving vibrational Schrödinger equation a posteriori. The potential of mean force (Pmf) was computed for the whole trajectory to derive the probability density distribution and for the O-H stretching mode from the proton vibrational eigenfunctions and eigenvalues incorporating statistical sampling and nuclear quantum effects. The electronic structure changes of the benzo[h]quinoline-2-methylresorcinol dimer and trimers were studied based on Constrained Density Functional Theory (CDFT) whereas the Electron Localization Function (ELF) method was applied for all systems. It was found that the bridged proton is localized on the donor side in both investigated systems in vacuo. The crystalline phase simulations indicated bridged proton-sharing and transfer events in HBQ. These effects are even more pronounced when nuclear quantization is taken into account, and the quantized Pmf allows the proton to sample the acceptor area more efficiently. The CDFT indicated the charge depletion at the bridged proton for the analyzed dimer and trimers in solvent. The ELF analysis showed the presence of the isolated proton (a signature of the strongest hydrogen bonds) only in some parts of the HBQ crystal simulation. The collected data underline the importance of the intramolecular coupling between the donor and acceptor moieties.

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Section: Constrained Density Functional Theory (Cdft) Electronic Structure Analysis Of Benzo[h]quinoline-2-methylresorcinol Dimer and Tricontrasting

confidence: 87%

Section: Constrained Density Functional Theory (Cdft) Electronic Structure Analysis Of Benzo[h]quinoline-2-methylresorcinol Dimer and Trimentioning

confidence: 90%

Section: Introductionmentioning

confidence: 99%

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Sensitivity of Intra- and Intermolecular Interactions of Benzo[h]quinoline from Car–Parrinello Molecular Dynamics and Electronic Structure Inspection

Panek

Zasada

Szyja

et al. 2021

IJMS

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“…The presence of intramolecular hydrogen bond is manifested by the structure stabilization as well as in the spectroscopic features, e.g., [ 30 , 31 , 32 ]. An interesting phenomenon associated with the hydrogen bond is proton transfer, which is significant in many processes at the molecular level, being responsible for structure changes and physico-chemical properties; see, e.g., [ 33 , 34 , 35 , 36 , 37 , 38 , 39 ]. The role of all intra- and intermolecular interactions has been intensively discussed because in many cases they are dynamic and their nature understanding is crucial in prediction and design of new compounds which could be novel drugs or materials.…”

Section: Introductionmentioning

confidence: 99%

Exploring Intra- and Intermolecular Interactions in Selected N-Oxides—The Role of Hydrogen Bonds

et al. 2022

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Intra- and intermolecular interactions have been explored in selected N-oxide derivatives: 2-(N,N-dimethylamino-N-oxymethyl)-4,6-dimethylphenyl (1) and 5,5’-dibromo-3-diethylaminomethyl-2,2’-biphenol N-oxide (2). Both compounds possess intramolecular hydrogen bonding, which is classified as moderate in 1 and strong in 2, and resonance-assisted in both cases. Density Functional Theory (DFT) in its classical formulation as well as Time-Dependent extension (TD-DFT) were employed to study proton transfer phenomena. The simulations were performed in the gas phase and with implicit and explicit solvation models. The obtained structures of the studied N-oxides were compared with experimental data available. The proton reaction path was investigated using scan with an optimization method, and water molecule reorientation in the monohydrate of 1 was found upon the proton scan progress. It was found that spontaneous proton transfer phenomenon cannot occur in the electronic ground state of the compound 1. An opposite situation was noticed for the compound 2. The changes of nucleophilicity and electrophilicity upon the bridged proton migration were analyzed on the basis of Fukui functions in the case of 1. The interaction energy decomposition of dimers and microsolvation models was investigated using Symmetry-Adapted Perturbation Theory (SAPT). The simulations were performed in both phases to introduce polar environment influence on the interaction energies. The SAPT study showed rather minor role of induction in the formation of homodimers. However, it is worth noticing that the same induction term is responsible for the preference of water molecules’ interaction with N-oxide hydrogen bond acceptor atoms in the microsolvation study. The Natural Bond Orbital (NBO) analysis was performed for the complexes with water to investigate the charge flow upon the polar environment introduction. Finally, the TD-DFT was applied for isolated molecules as well as for microsolvation models showing that the presence of solvent affects excited states, especially when the N-oxide acceptor atom is microsolvated.

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“…This not only forms two distinct quasi-rings in the structure, but also allows the opportunity to study the effects of substitution in the fused rings and double hydrogen bonding properties [58]. In case of the naphthazarin and its selected derivatives, investigations into physico-chemical properties are reported by [59][60][61]. The computational studies have been also used to assess compatibility of experimental and theoretical data in the IR and Raman spectra of naphthazarin, which in turn allowed precise assignment of bands [62].…”

Section: Introductionmentioning

confidence: 99%

Naphthazarin Derivatives in the Light of Intra- and Intermolecular Forces

et al. 2021

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Our long-term investigations have been devoted the characterization of intramolecular hydrogen bonds in cyclic compounds. Our previous work covers naphthazarin, the parent compound of two systems discussed in the current work: 2,3-dimethylnaphthazarin (1) and 2,3-dimethoxy-6-methylnaphthazarin (2). Intramolecular hydrogen bonds and substituent effects in these compounds were analyzed on the basis of Density Functional Theory (DFT), Møller–Plesset second-order perturbation theory (MP2), Coupled Clusters with Singles and Doubles (CCSD) and Car-Parrinello Molecular Dynamics (CPMD). The simulations were carried out in the gas and crystalline phases. The nuclear quantum effects were incorporated a posteriori using the snapshots taken from ab initio trajectories. Further, they were used to solve a vibrational Schrödinger equation. The proton reaction path was studied using B3LYP, ωB97XD and PBE functionals with a 6-311++G(2d,2p) basis set. Two energy minima (deep and shallow) were found, indicating that the proton transfer phenomena could occur in the electronic ground state. Next, the electronic structure and topology were examined in the molecular and proton transferred (PT) forms. The Atoms In Molecules (AIM) theory was employed for this purpose. It was found that the hydrogen bond is stronger in the proton transferred (PT) forms. In order to estimate the dimers’ stabilization and forces responsible for it, the Symmetry-Adapted Perturbation Theory (SAPT) was applied. The energy decomposition revealed that dispersion is the primary factor stabilizing the dimeric forms and crystal structure of both compounds. The CPMD results showed that the proton transfer phenomena occurred in both studied compounds, as well as in both phases. In the case of compound 2, the proton transfer events are more frequent in the solid state, indicating an influence of the environmental effects on the bridged proton dynamics. Finally, the vibrational signatures were computed for both compounds using the CPMD trajectories. The Fourier transformation of the autocorrelation function of atomic velocity was applied to obtain the power spectra. The IR spectra show very broad absorption regions between 700 cm−1–1700 cm−1 and 2300 cm−1–3400 cm−1 in the gas phase and 600 cm−1–1800 cm−1 and 2200 cm−1–3400 cm−1 in the solid state for compound 1. The absorption regions for compound 2 were found as follows: 700 cm−1–1700 cm−1 and 2300 cm−1–3300 cm−1 for the gas phase and one broad absorption region in the solid state between 700 cm−1 and 3100 cm−1. The obtained spectroscopic features confirmed a strong mobility of the bridged protons. The inclusion of nuclear quantum effects showed a stronger delocalization of the bridged protons.

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On the nature of inter- and intramolecular interactions involving benzo[h]quinoline and 10-hydroxybenzo[h]quinoline: Electronic ground state vs excited state study

Cited by 7 publications

References 60 publications

Sensitivity of Intra- and Intermolecular Interactions of Benzo[h]quinoline from Car–Parrinello Molecular Dynamics and Electronic Structure Inspection

Sensitivity of Intra- and Intermolecular Interactions of Benzo[h]quinoline from Car–Parrinello Molecular Dynamics and Electronic Structure Inspection

Exploring Intra- and Intermolecular Interactions in Selected N-Oxides—The Role of Hydrogen Bonds

Naphthazarin Derivatives in the Light of Intra- and Intermolecular Forces

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