Yuxi Sun

Experimental and theoretical studies on o-, m- and p-chlorobenzylideneaminoantipyrines.

Three antipyrine derivatives of o-, m- and p-chlorobenzylideneaminoantipyrines were characterized by spectral techniques and density functional calculations. The optimized configurations are very close to the XRD values and are used as foundations to investigate the molecular properties. The spectral assignments were attempted to ascribe to the vibrational modes of the detailed substructures with the aid of theoretical calculations because of the satisfactory consistencies between the experimental and theoretical spectra for each of the studied compounds. Raman spectral ascriptions represent that the pi-conjugated moieties linked by Schiff base imines are responsible for the excellent Raman scattering activities of these compounds. The linear polarizabilities and first hyperpolarizabilities of the studied molecules indicate that the compounds are good candidates of nonlinear optical materials. The statistical thermodynamic functions and their correlations with temperatures obtained from the theoretical vibrations are similar to each other among the isomers.

Experimental and density functional studies on 4-(4-cyanobenzylideneamino)antipyrine

4-(4-cyanobenzylideneamino)antipyrine (CBAP) has been synthesized and characterized by elemental analysis, FT-IR, UV-VIS and X-ray single crystal diffraction techniques. Crystallographic study reveals that the compound adopts trans configuration about the Schiff base imine double bond. The substituted p-cyanophenyl ring indirectly linked to the pyrazoline ring by the C=N double bond is almost coplanar with the pyrazole ring, whereas the phenyl ring directly attached to the pyrazoline ring forms an effective dihedral angle. Density functional calculations have been carried out to optimize and to characterize the title compound by using B3LYP method at 6-31G(d) basis set. The calculated results show that the optimized geometry can well reproduce the crystal structural parameters and the theoretical vibrational frequencies show good agreement with experimental values. On the basis of theoretical vibrational analyses, the thermodynamic properties (standard heat capacities, standard entropies, and standard enthalpy changes) of the title compound at different temperatures have been calculated, revealing the correlations between , , and temperatures. The total molecular dipole moment, mean linear polarizability and mean first hyperpolarizability obtained by calculation are 3.4724 Debye, 40.154 Å3 and 4.5424 × 10−29 cm5/esu, respectively. Three absorption bands in UV-VIS are mainly derived from the contribution of bands π → π* and electrons transfer from HOMO to LUMO, LUMO + 1, LUMO + 2, respectively.

Experimental and theoretical studies on vibrational spectra of 4-(2-furanylmethyleneamino)antipyrine, 4-benzylideneaminoantipyrine and 4-cinnamilideneaminoantipyrine

This work deals with the IR and Raman spectroscopy of 4-(2-furanylmethyleneamino) antipyrine (FAP), 4-benzylideneaminoantipyrine (BAP) and 4-cinnamilideneaminoantipyrine (CAP) by means of experimental and quantum chemical calculations. The equilibrium geometries, harmonic frequencies, infrared intensities and Raman scattering activities were calculated by density functional B3LYP method with the 6-31G(d) basis set. The comparisons between the calculated and experimental results covering molecular structures, assignments of fundamental vibrational modes and thermodynamic properties were investigated. The optimized molecular geometries have been compared with the experimental data obtained from XRD data, which indicates that the theoretical results agree well with the corresponding experimental values. For the three compounds, comparisons and assignments of the vibrational frequencies indicate that the calculated frequencies are close to the experimental data, and the IR spectra are comparable with some slight differences, whereas the Raman spectra are different clearly and the strongest Raman scattering actives are relative tightly to the molecular conjugative moieties linked through their Schiff base imines. The thermodynamic properties (heat capacities, entropies and enthalpy changes) and their correlations with temperatures were also obtained from the harmonic frequencies of the optimized structures.

Vibrational spectroscopic study of o-, m- and p-hydroxybenzylideneaminoantipyrines.

Three structurally similar antipyrine derivatives of o-hydroxybenzylideneaminoantipyrine (o-HBAP), m-hydroxybenzylideneaminoantipyrine (m-HBAP) and p-hydroxybenzylideneaminoantipyrine (p-HBAP) were characterized by FT-IR, FT-Raman experimental techniques and density functional theoretical (DFT) calculations. The comparisons between the calculated and experimental results covering molecular structures, assignments of fundamental vibrational modes and thermodynamic properties were investigated. The optimized molecular geometries agree well with the corresponding experimental values by comparing with the XRD data. The comparisons and assignments of the vibrational frequencies indicate that the experimental spectra also coincide satisfactorily with those of theoretically simulated spectrograms except the hydrogen-bond coupling infrared vibrations, and compounds can be distinguished by the IR and Raman spectra due to the differences of the hydroxyl-substituted positions and molecular packing, and the strong Raman scattering activities of the compounds are tightly relative to the molecular conjugative moieties linked through the Schiff base imines. The thermodynamic functions and their correlations with temperatures were also obtained from the theoretical harmonic frequencies.

Structural, proton-transfer, thermodynamic and nonlinear optical studies of (E)-2-((2-hydroxyphenyl)iminiomethyl)phenolate.

Recently, the study of imine-bridged organics is interested in proton-transfer and photo-responsive material fields. Herein, we make a investigation on the structural, thermodynamic and nonlinear optical properties of (E)-2-((2-hydroxyphenyl)iminiomethyl)phenolate (HPIMP). The structural varieties of the studied compound are characterized by the X-ray single crystal diffraction and vibrational spectral techniques, as well as the vibrational spectral bands are precisely ascribed to the studied structure with the aid of DFT theoretical calculations. The experimental results of the FT-IR and X-ray measurements supply good proofs to reveal the proton-transfer procedures of HPIMP, and exhibit that the studied compound is a good proton-transfer model. In addition, the thermodynamic properties are obtained from the theoretical vibrations of the optimized HPIMP. The linear polarizability (α(0)) and first-order hyperpolarizabilities (β(0)) respectively present the values of 26.28 Å(3) and 7.41×10(-30) cm(5)/esu predicated theoretically by the DFT-B3lYP method at 6-31G(d) level, which indicates that the studied compound is a promising nonlinear optical material candidate.

Experimental and theoretical studies on 4-(2,4-dichlorobenzylideneamino)antipyrine and 4-(2,6-dichlorobenzylideneamino)antipyrine.

Two antipyrine derivates, with the same formula C(18)H(15)Cl(2)N(3)O, are structurally similar Schiff bases derived from the condensation of 2,4-dichlorobenzaldehyde or 2,6-dichlorobenzaldehyde and 4-aminoantipyrine in methanol solutions. The compounds were characterized by elemental analysis, FT-IR, FT-Raman and UV-vis techniques. Density functional calculations were performed to further optimize and characterize them. The calculated results indicate that the theoretical values show good agreements with experimental ones. They are similar in their IR spectra and different in their Raman spectra. The detailed vibrational and UV-vis absorption spectra of the compounds have been ascribed to their corresponding molecular structures and electrons orbital transitions. The statistical thermodynamic functions and their correlations with temperatures of the title compounds have been obtained from their theoretical vibrations of the optimized structures. The nonlinear optical and UV-vis properties indicate that the compounds are the promising photoelectronic materials.

Synthesis, structure, photo-responsive properties of 4-(2-fluorobenzylideneamino)antipyrine: A combined experimental and theoretical study

In this work, 4-(2-fluorobenzylideneamino)antipyrine (FBIAAP) was synthesized and characterized by elemental analysis, XRD, FT-IR, FT-Raman and UV-Vis techniques as well as density functional calculations. The studied molecule adopts a trans configuration about the imine CN bond, and adjacent molecules are linked through two kinds of weak hydrogen bonds to form supramolecular layered structures along the ab plane. Vibrational spectral analyses show that the benzene moiety directly attached to the central pyrazoline shows good vibrational isolation from the other moiety of pyrazole-imino-benzene presenting good vibrational resonances. UV-vis absorption bands mainly belong to n→π and π→π according to the electron transfer orbital assignments for the electron absorption spectrum of FBIAAP. The first-order hyperpolarizability of FBIAAP is 44.9 times that of urea theoretically. In addition, the thermodynamic properties were also obtained theoretically from the harmonic frequencies of the optimized structure.