Non-covalent interactions towards 2-(4-(2,2-dicyanovinyl) benzylidene)malononitrile packing polymorphism due to solvent effect. Experimental and theoretical spectroscopy approach

Castillo, Armando E.; Pérez–Gutiérrez, Enrique; Ceballos, Paulina; Venkatesan, P.; Thamotharan, Subbiah; Siegler, Maxime A.; Percino, M. Judith

doi:10.1016/j.molstruc.2022.134674

Cited by 5 publications

(12 citation statements)

References 82 publications

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“…There is a pair of red spots on the surface of molecule B of 2j corresponding to C–H⋅⋅⋅N interactions ( Figure 4G ). We also observed bright red spots in similar acrylonitrile derivatives near the cyano N atom that serves as an acceptor for intermolecular interactions ( Venkatesan et al, 2018 ; Udayakumar et al, 2019a , Udayakumar et al, 2019c , Udayakumar et al, 2019b , Udayakumar et al, 2020 ; Castillo et al, 202 3).…”

Section: Resultsmentioning

confidence: 66%

Weak noncovalent interactions in two positional isomers of acrylonitrile derivatives: inputs from PIXEL energy, Hirshfeld surface and QTAIM analyses

et al. 2023

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A single crystal X-ray diffraction analysis was performed on two positional isomers (m-tolyl and p-tolyl) of acrylonitrile derivatives, namely, (Z)-3-(4-(pyridin-2-yl) phenyl)-2-(m-tolyl) acrylonitrile (1) and (Z)-3-(4-(pyridin-2-yl)phenyl)-2-(p-tolyl) acrylonitrile (2). Compound 1 crystallized in the monoclinic P21/n space group with two crystallographically independent molecules. Compound 2 also possesses two crystallographically independent molecules and crystallized in the triclinic P-1 space group. The Hirshfeld surface analysis revealed that, in both isomers, intermolecular H⋅⋅⋅H/C/N contacts contribute significantly to the crystal packing. More than 40% of the contribution arises from intermolecular C–H⋅⋅⋅C(π) contacts. In both compounds, the relative contribution of these contacts is comparable, indicating that the positional isomeric effects are marginal. The structures in which these isomers are arranged in the solid state are very similar, and the lattice energies are also comparable between the isomers. The Coulomb-London-Pauli-PIXEL (CLP-PIXEL) energy analysis identified the energetically significant dimers. The strength of the intra- and intermolecular interactions was evaluated using the quantum theory of atoms in molecules approach. The UV-Vis absorbance in three different solvents (chloroform, ethanol, and ethyl acetate) for isomers 1 and 2 are very similar. This result is in good agreement with the time-dependent density-functional theory (TD-DFT) calculations.

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Section: Resultsmentioning

confidence: 66%

Weak noncovalent interactions in two positional isomers of acrylonitrile derivatives: inputs from PIXEL energy, Hirshfeld surface and QTAIM analyses

et al. 2023

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“…The harmonic spectra for FMISO, FETNIM, FETA and FAZA exhibit a distinct ν(CF) mode at 977, 992, 997 and 991 cm −1 . In all four cases, this band suffers a blue-shift of 5, 6, 11 and 9 cm −1 in the 18 F spectra with respect to the 19 F spectra. When comparing anharmonic frequencies, this difference decreases for FETNIM (3 cm −1 ), remains the same for FETA and increases for FMISO (6 cm −1 ) and FAZA (13 cm −1 ).…”

Section: -Nitroimidazole Derivativesmentioning

confidence: 83%

“…Next, we analyzed the calculated IR and Raman spectra (Figures S12-S16) for the five compounds in which the 19 F atom was replaced by the 18 F radioisotope. The calculations were performed for the most stable conformers in each case.…”

Section: -Nitroimidazole Derivativesmentioning

confidence: 99%

“…The computed NMR data were determined using the appropriate solvent specified in the respective available experimental works. Tetramethylsilane (TMS) was used as an NMR reference standard for FMISO (both for 1 H and 13 C spectra), FAZA (both for 1 H and 13 C spectra), FETA (for 1 H spectrum), EF5 (for 1 H spectrum) and for 2nim (both for 1 H and 13 C spectra), whereas the CFCl 3 or CF 3 COOH standards have been employed for 19 F nuclei, according to the experimental conditions. The calculated spin-spin couplings are reported merely where experimental values are available.…”

Section: Nmr Datamentioning

confidence: 99%

“…However, we have provided computational data for the chemical shifts and spin-spin couplings in Table S6 in the Supplementary Material for future reference. On the other hand, for the FMISO and FAZA compounds, a more substantial body of experimental NMR data has been amassed for the 1 H, 13 C and 19 F nuclei and therefore allow for a more detailed analysis.…”

Section: Nmr Datamentioning

confidence: 99%

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Exploring Geometrical, Electronic and Spectroscopic Properties of 2-Nitroimidazole-Based Radiopharmaceuticals via Computational Chemistry Methods

Crișan,

Stan,

Chiș

2024

Molecules

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Tumor hypoxia plays an important role in the clinical management and treatment planning of various cancers. The use of 2-nitroimidazole-based radiopharmaceuticals has been the most successful for positron emission tomography (PET) and single photon emission computed tomography (SPECT) imaging probes, offering noninvasive means to assess tumor hypoxia. In this study we performed detailed computational investigations of the most used compounds for PET imaging, focusing on those derived from 2-nitroimidazole: fluoromisonidazole (FMISO), fluoroazomycin arabinoside (FAZA), fluoroetanidazole (FETA), fluoroerythronitroimidazole (FETNIM) and 2-(2-nitroimidazol-1-yl)-N-(2,2,3,3,3-pentafluoropropyl)acetamide (EF5). Conformational analysis, structural parameters, vibrational IR and Raman properties (within both harmonic and anharmonic approximations), as well as the NMR shielding tensors and spin-spin coupling constants were obtained by density functional theory (DFT) calculations and then correlated with experimental findings, where available. Furthermore, time-dependent DFT computations reveal insight into the excited states of the compounds. Our results predict a significant change in the conformational landscape of most of the investigated compounds when transitioning from the gas phase to aqueous solution. According to computational data, the 2-nitroimidazole moiety determines to a large extent the spectroscopic properties of its derivatives. Due to the limited structural information available in the current literature for the investigated compounds, the findings presented herein deepen the current understanding of the electronic structures of these five radiopharmaceuticals.

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Small-Molecule:Polymer Composites for Transparent Films with Visible Emission

Pérez-Gutiérrez,

Calvo,

Beristain

et al. 2024

J Fluoresc

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The analysis of the shift in photoluminescence emission for a blend of polyvinylcarbazole and acrylonitrile derivative compounds is reported. The small-molecule compounds have different functional groups, phenyl, pyridine, or methyl phenyl, attached to an acrylonitrile group. According to the functional group, the blue emission for pure dye shifts to green or yellowish in the blend film. Several PVK:dye ratios from 0:100 to 20:80 were used for film deposition. The film morphology was analyzed by atomic force microscopy; for low dye content, homogeneous films were achieved. However, aggregates of several micrometers are formed on the surface of films with higher dye concentrations. The shift in emission occurs only with PVK, and for a non-conjugated matrix such as polystyrene, the emission remains unchanged. The interaction of dyes with PVK leading to change in emission was also achieved by grinding dye and polymer. Results showed that shifts in emission could come from exciplex formation along with changes in dye intermolecular interactions. The blend films were highly transparent in the visible spectra due to the absorption in the UV region for dye and matrix. The films with ratio PVK: dye ratio 80:20 was used as active layer in OLEDs.

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Non-covalent interactions towards 2-(4-(2,2-dicyanovinyl) benzylidene)malononitrile packing polymorphism due to solvent effect. Experimental and theoretical spectroscopy approach

Cited by 5 publications

References 82 publications

Weak noncovalent interactions in two positional isomers of acrylonitrile derivatives: inputs from PIXEL energy, Hirshfeld surface and QTAIM analyses

Weak noncovalent interactions in two positional isomers of acrylonitrile derivatives: inputs from PIXEL energy, Hirshfeld surface and QTAIM analyses

Exploring Geometrical, Electronic and Spectroscopic Properties of 2-Nitroimidazole-Based Radiopharmaceuticals via Computational Chemistry Methods

Small-Molecule:Polymer Composites for Transparent Films with Visible Emission

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