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1.
    
The NMR chemical shifts of the aromatic hydrogen atoms of 1‐n‐butyl‐3‐methylimidazolium tetrafluoroborate and 1‐n‐butyl‐3‐methylimidazolium hexafluorophosphate have been determined in nine deuterated solvents. The aromatic hydrogen atoms of are more sensitive to solvation effects than the hydrogen atoms of . The interaction of the hydrogen atoms of the imidazolium cation with the relatively small and basic anion is more intimate than the interaction with the fairly large, polarizable and less basic anion. For both salts, the interaction involving the anion and the hydrogen atoms of the imidazolium cation is more intimate for H2, compared with H4 or H5. Owing to the intimate interaction of the ions of , its aromatic hydrogen atoms are less sensitive to solvation effects than the hydrogen atoms of . Copyright © 2001 John Wiley & Sons, Ltd.  相似文献   

2.
    
Anionic species formed in mixtures of 1‐n‐butyl‐3‐methylimidazolium chloride (BMICl) with different amounts of niobium pentachloride (NbCl5) or zinc dichloride (ZnCl2) were investigated by Raman spectroscopy. In the BMICl and NbCl5 ionic mixtures the presence of the anion NbCl6− was detected for all compositions (molar fraction, X) and a mixture of this anion and the neutral Nb2Cl10 in acid ones. Two different anions were observed for basic mixtures of BMICl and ZnCl2: ZnCl42−(0 < X < 0.35) and Zn2Cl62−(X > 0.3), whereas for acidic ones three species were detected: Zn2Cl62−(X < 0.7), Zn3Cl82−(X > 0.7) and Zn4Cl102−(X > 0.7). It has also been observed that in both cases, the formation of larger anions causes a shift of the C H stretching modes to higher wavenumbers as the result of a decrease in the hydrogen bond between Cl and the hydrogens from the cation. Copyright © 2008 John Wiley & Sons, Ltd.  相似文献   

3.
    
A computationally‐assisted methodology to assign the vibrational spectra of molecular materials (PiMM) has been successfully applied to the Raman and infrared (IR) spectra of trans‐cinnamic acid (t‐CIA) in the solid state. The effects of molecular association through O H···O hydrogen‐bonding in both the wavenumber and the intensity of the bands are accurately described by a single dimer structure. This supports the discrimination between the possible conformers in the solid, the complete evaluation of hydrogen‐bonding effects, and the full assignment of the vibrational spectra of t‐CIA. Copyright © 2008 John Wiley & Sons, Ltd.  相似文献   

4.
    
The Raman and Infrared (IR) spectra of poly(methyl methacrylate) (PMMA) membranes plasticized by ionic liquids of the (1 − x)[1‐butyl‐3‐methylimidazolium bis(trifluoromethanesulfonyl)imide (BMITFSI)],xLiTFSI type, where BMI+ is the 1‐butyl‐3‐methylimidazolium cation and TFSI− the bis(trifluoromethanesulfonyl)imide anion, are analyzed for a lithium bis(trifluoromethane sulfone)imide (LiTFSI) mole fraction x = 0.23 and PMMA contents from 0 to 50 wt%. The lithium is found to have an average coordination of about three CO groups and less than one TFSI− anion. It plays the role of a cross‐linker between the ester groups of PMMA and the nonvolatile ionic liquid. Addition of PMMA to the (1 − x)(BMITFSI),xLiTFSI ionic liquid lowers the conductivity but might improve the lithium transference number by transforming the [Li(TFSI)2]− anionic clusters present in the pure ionic liquid into a mixed coordination by ester groups and TFSI− anions. Copyright © 2008 John Wiley & Sons, Ltd.  相似文献   

5.
    
The IR and Raman spectra of ethyl salicylate were recorded and analyzed. The surface enhanced Raman scattering (SERS) spectrum was recorded in a silver colloid. The vibrational wavenumbers of the compound have been computed using the Hartree‐Fock/6‐31G* basis. The direction of charge transfer contribution to SERS has been discussed from the frontier orbital theory. The presence of methyl modes in the SERS spectrum indicates the nearness of the methyl group to the metal surface and the presence of ring vibrations and out‐of‐plane ring modes in the SERS spectrum suggests a flat orientation of the molecule on the silver surface. The first hyperpolarizability is calculated and the calculated molecular geometry has been compared with the reported similar structures. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

6.
    
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7.
    
The S3− radical anion is observed in several systems: non‐aqueous polysulfides solutions, doped alkali halides, ultramarine pigments (UP) for which S3− is the blue chromophore and S2− is the yellow one and pigments of zeolite 4A structure. The S3− ion has C2V symmetry, and therefore its three vibrational modes should be observed in the Raman and in IR spectra. In resonance Raman spectroscopy, only the symmetric stretching mode ν1 and the bending mode ν2 have been observed, whereas the anti‐symmetric stretching mode ν3 has never been observed whatever the system. In this work, we confirm that ν3 is not observed in solutions with resonance Raman spectroscopy. However, our investigation of several blue UP, with various concentrations of S2−, shows that there is a superposition of two bands at ca 590 cm−1: the first is assigned to ν (S2−) and the second to ν3 (S3−). With the 457.9 nm excitation line, for which the resonance conditions are simultaneously fulfilled for S2− and S3−, the band at ca 590 cm−1 is the sum of the contributions of both ν (S2−) and ν3 (S3−) vibrations, while, with the 647.1 nm line, which only satisfies the resonance conditions of S3−, the band at ca 584 cm−1 must be assigned only to ν3 (S3−). Furthermore, ν3 (S3−) is observed in green UP and in pigments of zeolite structure. The ν3 vibration of S3−, which is observed neither in polysulfide solutions nor in doped alkali halides in resonance Raman conditions, can therefore be observed when this species is inserted into the β‐cages of the sodalite or of the zeolite 4A structures. So, the band at ca 590 cm−1 cannot always be assigned to S2− in these systems. This implies that the concentration of S2− in UP must be reconsidered. Copyright © 2007 John Wiley & Sons, Ltd.  相似文献   

8.
    
The FT‐IR and FT‐Raman spectra of anilinium sulfate were recorded and analyzed. The surface‐enhanced Raman scattering (SERS) was recorded from a silver electrode. The vibrational wavenumbers of the compound have been computed using the Hartree‐Fock/6‐31G* basis and compared with the experimental values. The molecule is adsorbed on the silver surface with the benzene ring in a tilted orientation. The presence of amino and sulfate group vibrations in the SERS spectrum reveal the interaction between amino and sulfate groups with the silver surface. The direction of the charge transfer contribution to SERS has been discussed from the frontier orbital theory. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

9.
    
The inclusion compounds of α‐, β‐ and γ‐cyclodextrins (α‐CD, β‐CD and γ‐CD) with trans‐cinnamic acid (t‐CIA), 3‐hydroxy‐trans‐cinnamic acid (t‐3OHCIA), 4‐hydroxy‐trans‐cinnamic acid (t‐4OHCIA) and 3,4‐dihydroxy‐trans‐cinnamic acid (t‐3,4OHCIA) were prepared and characterized, in the solid state, by means of thermogravimetry and Raman spectroscopy. The effects of the inclusion process on the guest molecules and on the hydrogen bond interactions of the guest were studied by monitoring sensitive vibrational modes, such as CO, CC and ring C H stretching modes. By combining Raman and TG data with ab initio calculations and information from CSD database on similar compounds, inclusion geometries for the different compounds are proposed. The size of the host cavity and the maximization of host/guest hydrogen‐bonding contacts appear to be the main factors determining the inclusion geometries. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

10.
    
Quantum chemical calculations of energies, geometries and vibrational wavenumbers of 2,4‐difluorophenol (2,4‐DFP) were carried out by using ab initio HF and density functional theory (DFT/B3LYP) methods with 6‐311G(d,p) as basis set. The optimized geometrical parameters obtained by HF and DFT calculations are in good agreement with related molecules. The best level of theory in order to reproduce the experimental wavenumbers is the B3LYP method with the 6‐311G(d,p) basis set. The difference between the observed and scaled wavenumber values of most of the fundamentals is very small. A detailed interpretation of the infrared and Raman spectra of 2,4‐DFP is also reported. The entropy of the title compound was also performed at HF/6‐311G(d,p) and B3LYP/6‐311G(d,p) levels of theory. The isotropic chemical shift computed by 1H, 13C NMR analyses also shows good agreement with experimental observations. The theoretical spectrograms for FT‐IR and FT‐Raman spectra of the title molecule have been constructed. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

11.
    
The Fourier‐transform infrared and Fourier‐tranform Raman spectra of phenyl phosphate disodium salt were recorded and analyzed. The surface‐enhanced Raman scattering (SERS) spectrum was recorded in a silver colloid. The vibrational wavenumbers of the compound were computed using the Hartree–Fock/6‐31G* basis and compared with the experimental values. The molecule is adsorbed on the silver surface with the benzene ring in a tilted orientation. The presence of the phenyl ring and the phosphate group vibrations in the SERS spectrum reveal the interactions between the phenyl ring and the phosphate group with the silver surface. The first hyperpolarizability is calculated, and the calculated molecular geometry is compared with those of similar reported structures. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

12.
    
Investigations of the vibrational spectra of cyclo(Gly‐Gly), cyclo(L‐Ala‐L ‐Ala) and cyclo(L ‐Ala‐Gly) are reported. Raman scattering and Fourier transform infrared (FTIR) spectra of solid‐state and aqueous protonated samples, as well as their corresponding N‐deuterated isotopomers, have been examined. In addition, density functional theory (DFT) (B3‐LYP/cc‐pVDZ) calculations of molecular structures and their associated vibrational modes were carried out. In each case, the calculated structures of lowest energy for the isolated gas‐phase molecules have boat conformations. Assignments have been made for the observed Raman and FTIR vibrational bands of the cyclic di‐amino acid peptides (CDAPs) examined. Raman polarization studies of aqueous phase samples are consistent with C2 and C1 symmetries for the six‐membered rings of cyclo(L‐Ala‐L‐Ala) and cyclo(L‐Ala‐Gly), respectively. There is a good correlation between experimental and calculated vibrational bands for the three CDAPs. These data are in keeping with boat conformations for cyclo(L‐Ala‐L‐Ala) and cyclo(L‐Ala‐Gly) molecules, predicted by the ab initio calculations, in both the solid and aqueous solution states. However, Raman spectroscopic results might infer that cyclo(L‐Ala‐Gly) deviates only slightly from planarity in the solid state. The potential energy distributions of the amide I and II modes of a cis‐peptide linkage are shown to be significantly different from those of the trans‐peptides. For example, deuterium shifts have shown that the cis‐amide I vibrations found in cyclo(Gly‐Gly), cyclo(L‐Ala‐L‐Ala), and cyclo(L‐Ala‐Gly) have larger N‐H contributions compared to their trans‐amide counterparts. Compared to trans‐amide II vibrations, cis‐amide II vibrations show a considerable decrease in N H character. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

13.
    
Experimental vibrational spectroscopic studies and density functional theory (DFT) calculations of the di‐amino acid peptide derivatives α‐ and β‐N‐acetyl‐L‐Asp‐L‐Glu have been undertaken. Raman and infrared spectra have been recorded for samples in the solid state. DFT simulations were conducted using the B3‐LYP correlation functional and the cc‐pVDZ basis set to determine energy minimized/geometry optimized structures (based on a single isolated molecule in the gaseous state). Normal coordinate calculations have provided vibrational assignments for fundamental modes, including their potential energy distributions. Significant differences are observed between α‐ and β‐N‐acetyl‐L‐Asp‐L‐Glu both in the computed structures and in the vibrational spectra. The combination of experimental and calculated spectra provide an insight into the structural and vibrational spectroscopic properties of di‐amino acid peptide derivatives. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

14.
    
The Fourier transform infrared (FT‐IR) and FT‐Raman spectra of sulfur trioxide‐pyridine complex were recorded and analyzed. The potential‐dependent surface‐enhanced Raman scattering (SERS) was recorded from an electrochemically roughened silver electrode. The vibrational wave numbers of the compound were computed using the Hartree–Fock/6‐31G* basis and compared with the experimental values. The presence of strong pyridine ring vibrations in the SERS spectrum reveals the interaction between the pyridine ring and the silver surface. The molecule is adsorbed on the silver surface with the pyridine ring in a tilted orientation. The direction of charge‐transfer contribution to the SERS is discussed from the frontier orbital theory. The value of the calculated first hyperpolarizability is comparable to those reported for similar structures, which makes this molecule an attractive object for future studies of nonlinear optics. The optimized geometrical parameters of the title compound are in agreement with similar reported structures. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

15.
    
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16.
    
Two α‐cyanohydroxycinnamic acid positional isomers, α‐cyano‐4‐hydroxycinnamic acid (CHCA4) and α‐cyano‐3‐hydroxycinnamic acid (CHCA3), were characterized by using Raman spectroscopy. We analysed the implications of the collected Raman spectral shifts, and verified them through other spectroscopic techniques, to arrive at plausible three dimensional structures of CHCA3 and CHCA4. The positions of these groups were mapped by systematically analysing the orientation and type of interactions functional groups make in each CHCA isomer. We determined whether or not the carboxylic moieties are forming dimeric links and ascertained the existence of ring–ring π‐stacking interactions. We also assessed the nature of the hydrogen bonding between –CN and –OH groups. The results were then taken together to model plausible three‐dimensional structures for each compound. The data revealed a structure for CHCA4 that matches the published X‐ray crystallographic structure. We then applied the same spectral analysis to CHCA3 to reveal its plausible three‐dimensional structure. The structural details revealed may account for the functional properties of the two α‐cyanohydroxycinnamic acid positional isomers. Copyright © 2017 John Wiley & Sons, Ltd.  相似文献   

17.
    
Infrared (IR) and Raman spectra were obtained for N,N′‐dicyclohexylcarbodiimide (DCC) in the solid state and in CHCl3 solution. Structures and vibrational spectra of isolated, gas‐phase DCC molecules with C2 and Ci symmetries, computed at the B3‐LYP/cc‐pVTZ level, show that the IR and Raman spectra provide convincing evidence for a C2 structure in both the solid state and in CHCl3 solution. Using a scaled quantum‐chemical force field, these density functional theory calculations have provided detailed assignments of the observed IR and Raman bands in terms of potential energy distributions. Comparison of solid‐state and solution spectra, together with a Raman study of the melting behaviour of DCC, revealed that no solid‐state effects were evident in the spectra. Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   

18.
    
Theoretical studies on the thermolysis in the gas phase of three methyl β‐hydroxycarboxylates RR′C(OH)CH2COOCH3, methyl 3‐hydroxypropanoate (primary alcohol, I ), methyl 3‐hydroxybutanoate (secondary alcohol, II ) and methyl 3‐hydroxy‐3‐methylbutanoate (tertiary alcohol, III ), were carried out using ab initio theoretical methods at the MP2/6–31G(d) and MP2/6–311+G(d,p) levels of theory. The pathways describe a mechanism via a six‐membered cyclic transition state, with the formation of an aldehyde or a ketone and an enol intermediate, followed by the tautomerization of this intermediate to methyl acetate. The progress of the reactions was followed by means of the Wiberg bond indices. The results indicate that the transition states are late, and the proton transfer is the more advanced process. The kinetic parameters calculated for the reactions studied agree well with the available experimental results. A theoretical study on the kinetic deuterium isotope primary and α‐ and β‐secondary effects was also carried out. Copyright © 2004 John Wiley & Sons, Ltd.  相似文献   

19.
    
The tautomeric equilibria between the CH, OH and NH forms in a series of 4‐substituted 1‐phenyl‐3‐methyl‐pyrazolin‐5‐ones have been studied using ab initio calculations at various levels of theory and comparison made with the experimental results obtained from NMR measurements. Quantitative comparison of both the relative energies and the 13C chemical shifts of the tautomers constituting the tautomeric equilibria were made by calculation of both sets of parameters. The influence of the solvent was included by employing various models of the self‐consistent reaction field theory. Initially, the solvent was included in the calculations by applying a continuum of differing polarity over the surface of isolated tautomers (self‐consistent isodensity polarized continuum model method), then later by assuming formation of an adduct between the solute and the solvent (thereby simulating effectively the hydrogen bonding in the OH and NH tautomers) and finally by calculating dimer or trimer complexes of the various tautomers. In this manner, the agreement between the theoretically calculated and the experimentally determined tautomeric equilibria was improved significantly. The theoretically calculated 13C chemical shifts of the tautomers were found to be viable for the assignment of the tautomers, particularly the preferred tautomer in the OH/NH equilibrium, which remains fast on the NMR time scale even at low temperatures. Copyright © 2001 John Wiley & Sons, Ltd.  相似文献   

20.
    
In this paper we describe the unprecedented reaction between α‐diazo esters 1 and iodine. The reaction, carried out in the presence of aqueous NaHCO3, afforded the Z‐isomer of the corresponding unsaturated‐2‐iodo ester 8 . The configuration of compounds 8 was determined using the 3JC? H coupling between carbonyl carbon atom and alkene proton. Mechanistic considerations accounting for the observed phenomena and including quantum chemical calculations are proposed. Copyright © 2008 John Wiley & Sons, Ltd.  相似文献   

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