Effect of cation-anion interactions on the structural and vibrational properties of 1-buthyl-3-methyl imidazolium nitrate ionic liquid

Kausteklis, Jonas; Aleksa, Valdemaras; Iramain, Maximiliano Alberto; Brandán, Silvia Antonia

doi:10.1016/j.molstruc.2018.03.100

Cited by 42 publications

(12 citation statements)

References 30 publications

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“…In this spectral zone (Figure .5) we observe a spectrum with high density for the Clanion than for the H 2 PO 4 anion. We notice the mode in 1347 cm -1 for the Clanion which is transformed for the H 2 PO 4 anion to 1360 and 1338 cm -1 modes (Imidazolium ring: C-N, C=N str, CH 2 (N) str, CH 3 (N) CN Str, ν (C-C)) [21,26,29,40].We also observe in 1338 cm -1 the presence of the stretching mode P=O forH 2 PO 4 anion [36].The spectral zone of the CH 2 rockingof the cation [EtOHMIM + ]1500-1400also seems to be influenced by the choice of the anion in a less important way. In the spectral zone 1800-1500 cm -1 , we observe a shift in frequency of the vibrational mode attributed to the ring C=C and =C-H stretching [21,32].…”

Section: 23region 1800-1300 CM -1mentioning

confidence: 93%

“…In this spectral region (Figure .6), we observe more peaks for the Clanion than for the H 2 PO 4 anion. In the spectral range 3000-2600 cm -1 , we observe the vibrational mode attributed to the symmetric and antisymmetric (CH 2 ) of the cation [EtOHMIM + ] [21,29]. The C-H ring stretching occurs in the regions 3100-3000 cm -1 which is the characteristic region of the ready identification of the C-H stretching vibrations [41].The vibrational mode of the(C-H)is observed in the spectral range: 2993, 3035, 3051, 3097 cm -1 and 3140 cm -1 for the anion Cland at 3111 and 3157 cm -1 for the anion H 2 PO 4 -.We notice the mode in 3140 cm -1 for the Clanion which is transformed for the H 2 PO 4 anion to 3111 and 3157 cm -1 modes (H-C-C-H asym str, ν as (C-H), CH 3 (N), = C-H stretching) [21,26,29,40,41].Note that the presence of a shoulder intensity predicted at 3311 cm -1 can be assigned to the corresponding vibrational mode OH (alcohol function of the cation) and possibly OH of H 2 PO 4 anion [42]. ]…”

Section: Region 3500-2400 CM -1mentioning

confidence: 99%

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Synthesis, vibrational and thermal properties of new functionalized 1- (2-hydroxyethyl) -3-methylimidazolium dihydrogenophosphate ionic liquid

Zaoui¹,

Debdab²,

Haddad³

et al. 2021

Journal of Molecular Structure

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Very recently, the hydroxyl-functionalized ionic liquids have gained immense interest and were developed for a number of interesting applications.In this work and for the first time new hydroxyl-functionalizedwas synthesized in our laboratory. The synthesis is based on an alkylation reaction of 1-methylimidazole followed by anion exchange. The obtained IL is characterized by 1 H-NMR, 13 C-NMR spectroscopy. This experimental vibrational spectroscopy have been investigated using Infrared and Raman spectroscopy, based on the infrared (IR) and Raman spectroscopies results, complete vibrational assignments have been performed. Besides, thermal properties of this hydroxyl-functionalized IL were investigated by using following techniques, (i) Thermogravimetric Analysis (TGA) and Derivative Thermogravimetry (DTG) in the temperature range from 20 to 600 C°, (ii) differential scanning calorimetry (DSC) from-100 °C to 200 °C. The thermogravimetry analysis was coupled with mass spectrometry in order to assess the influence of anion on the measured property.

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Section: 23region 1800-1300 CM -1mentioning

confidence: 93%

Section: Region 3500-2400 CM -1mentioning

confidence: 99%

Synthesis, vibrational and thermal properties of new functionalized 1- (2-hydroxyethyl) -3-methylimidazolium dihydrogenophosphate ionic liquid

Zaoui¹,

Debdab²,

Haddad³

et al. 2021

Journal of Molecular Structure

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“…were calculated in BCPs and RCPs by using the B3LYP/6-31G* method, as in similar species containing rings [1,[3][4][5][6][7][8][9][10][11][12][13][14][15]. These properties for corticosterone in all media are presented in Table 6.…”

Section: Nbo and Aim Studiesmentioning

confidence: 99%

“…The combination of theoretical density functional theory (DFT) calculations by using hybrid B3LYP methods with different experimental spectroscopic techniques is a very good methodology to elucidate reliably and effectively structural, electronic, topological and vibrational properties of diverse compounds [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15]. The use of this methodology in species containing fused rings such as alkaloids, antihistaminic agents and species steroids, has allowed the optimizations of theoretical structures and the determination of their properties [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15] while the complete assignments of all bands observed in the experimental infrared and Raman spectra were possible by using the normal internal coordinates, the SQMFF methodology and the Molvib program [16][17][18]. Now, the identifications of cocaine, heroin, morphine and scopolamine alkaloids [1,[3][4][5]7], of antihistaminic agents promethazine [8] and of equilenin, equilin and estrone steroids [9] can be easily carried out in all media by using vibrational spectroscopy.…”

Section: Introductionmentioning

confidence: 99%

Investigating the behaviors of corticosterone hormone in different solvents by using DFT calculations and experimental data

2019

Biointerface Res Appl Chem

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In this work, structural, electronic, topological and vibrational properties of corticosterone hormone have been investigated in aqueous, ethanol and methanol solutions by using DFT calculations and experimental available infrared, attenuated total reﬂectance (ATR), Raman and Ultraviolet spectra. The properties predicted in the different solvents at the B3LYP/6-31G* level of theory were compared with those obtained in gas phase and, with others reported for steroids species at the same level of theory. The universal solvation model has evidenced higher solvation energy for corticosterone in aqueous solution and a higher value in methanol, as compared with the corresponding values to equilenin, equilin and estrone steroids in the same medium. Higher Mulliken charges on O atoms of C=O group of side chain are observed in the three solvents than the corresponding to C=O group of ring A while the MK charges on O atoms of OH group of ring C present higher values than the corresponding to O atoms of OH group of side chain. The natural bond orbital (NBO) studies have revealed a low stability of corticosterone in aqueous solution, as compared with the values in ethanol and methanol solutions, in total agreement with the higher solvation energy and dipole moment in this medium. On the other hand, the atoms in molecules (AIM) analyses support the lower stabilities of corticosterone in the three solutions because only five H bonds interactions different from of gas phase where six interactions are observed. The gap values suggests that corticosterone is most reactive in aqueous solution than the other solutions, as supported by the low stability and higher solvation energy and dipole moment values in this medium. This study shows clearly that the steroid species most reactive, equilenin and corticosterone, are characterized by a high global electrophilicity index value and low nucleophilicity index. Reasonable correlations in the predicted IR, Raman and UV spectra were observed, as compared with the corresponding experimental ones. Additionally, the complete vibrational assignments of all 159-vibration modes of corticosterone together with the harmonic force fields and force constants in the different media are for the first time presented.

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“…DFT calculations are very useful tools to analyse structures and predict properties of numerous compounds with different fused rings [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15], such as tropane alkaloids. These alkaloids contain the >N-CH 3 group and present a wide range of biological properties and different structural, electronic and topological properties some of which were studied by our research group [1][2][3][4][5][6][7].…”

Section: Introductionmentioning

confidence: 99%

DFT study of species derived from the narcotic antagonist naloxone

2020

Biointerface Res Appl Chem

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The functional hybrid B3LYP and the 6-31G* basis set have been employed to study the theoretical structures of free base, cationic and hydrochloride species of naloxone in gas phase and in aqueous solution. The SCRF methodology and the PCM method were used to optimize the species in solution while the solvation energies were computed with the universal solvation model. The harmonic force fields of three species in the two media were computed with the SQMFF methodology and the Molvib program while the complete vibrational assignments of bands observed in the experimental available ATR and Raman spectra were performed by using the harmonic force fields and the normal internal coordinates. Therefore, the expected 129, 132 and 135 vibration normal modes for the free base, cationic and hydrochloride species of naloxone, respectively are here reported. The free base of naloxone evidence the higher solvation energy value, as compared with those reported for S(-)-promethazine, R(+)-promethazine, cyclizine, morphine, cocaine, scopolamine, heroin, and tropane alkaloids. The cationic species shows a solvation energy value (-302.45 kJ/mol) closer to observed for morphine (-309.19 kJ/mol) while the value for the hydrochloride species (-122.28 kJ/mol) is near to scopolamine value (-122.74 kJ/mol). AIM analyses show ionic characteristic of N-HCl bonds in the hydrochloride species and suggest that this species in both media is as cationic one, as supported by the positive MK charges on the N5 atoms in the hydrochloride species in both media and by the absence in the ATR spectrum of band at 2405 cm-1, associated to N5-H46 stretching mode. Moreover, frontier orbitals studies evidence that the allyl chains present in the three species of naloxone diminishing the gap values increasing their reactivities, as compared with the other species containing the N-CH3 group. The f(N-H) force constants for the hydrochloride species is lower than the corresponding in solution, a result also observed for morphine (2.73 and 4.61 mdyn Å-1), cocaine (3.23 and 4.79 mdyn Å-1) and tropane (2.70 and 4.69 mdyn Å-1) alkaloids. Comparisons between experimental infrared, Raman and ultraviolet-visible spectra with the corresponding predicted show good correlations.

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Effect of cation-anion interactions on the structural and vibrational properties of 1-buthyl-3-methyl imidazolium nitrate ionic liquid

Cited by 42 publications

References 30 publications

Synthesis, vibrational and thermal properties of new functionalized 1- (2-hydroxyethyl) -3-methylimidazolium dihydrogenophosphate ionic liquid

Synthesis, vibrational and thermal properties of new functionalized 1- (2-hydroxyethyl) -3-methylimidazolium dihydrogenophosphate ionic liquid

Investigating the behaviors of corticosterone hormone in different solvents by using DFT calculations and experimental data

DFT study of species derived from the narcotic antagonist naloxone

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