The rovibrational spectra of thioanisole(TA)and its halogenated derivatives,3-fluorothioanisole(3FTA)and 3-chlorothioanisole(3ClTA),were measured using synchrotron-based Fourier transform infrared spectroscopy(FTIR)at...The rovibrational spectra of thioanisole(TA)and its halogenated derivatives,3-fluorothioanisole(3FTA)and 3-chlorothioanisole(3ClTA),were measured using synchrotron-based Fourier transform infrared spectroscopy(FTIR)at the Canadian Light Source.Combined with density functional theory calculations,the stable structures and vibrational modes of TA,3FTA,and 3ClTA in their vibrational states were analyzed.The theoretical vibrational mode frequencies were corrected by simulating the rotational structure of a vibrational band.The contributions of the cis-and trans-isomers of 3FTA and 3ClTA to the FTIR spectra at 298 K were estimated using the Boltzmann distribution,revealing their coexistence in the experimental spectra.The results indicate that both fluorine and chlorine substitution significantly affect the vibrational modes,particularly in the benzene ring.Compared to TA,the FTIR spectra of 3FTA and 3ClTA show changes in the frequencies and intensities of some vibrational modes,with halogen substitution causing specific modes to shift to higher wavenumbers.A comparison of the FTIR spectra of TA,3FTA,and 3ClTA highlights the influence of halogen substitution on vibrational properties,emphasizing how the type and position of the substituent affect frequency shifts and spectral intensities.These findings provide deeper insights into how halogenation alters vibrational spectra,which is crucial for further spectral analysis and molecular structure determination.展开更多
Self Assembled Monolayers(SAMs) of a series of mercapto contained azobenzene derivatives with the structure of C n H 2 n +1 AzoO(CH 2) m SH (where n =4,6,8,10,12; with m =3,5 respectively) were prepared and characteri...Self Assembled Monolayers(SAMs) of a series of mercapto contained azobenzene derivatives with the structure of C n H 2 n +1 AzoO(CH 2) m SH (where n =4,6,8,10,12; with m =3,5 respectively) were prepared and characterized.Wettability measurement of water on the SAMs demonstrates that molecular packing density in the monolayers increases while the alkyl chain in the molecules is lengthened. Both the n and m values have similar contribution to the wetting property of SAMs. The RA IR spectra reveal that the alkyl chains in the SAMs tilt away dramatically from the surface normal direction with the increase in their length. However, the orientation of azobenzene moiety is found to be influenced slightly by the alkyl chain length, which is due to the tenderness of the molecule.展开更多
基金supported by the National Natural Science Foundation of China(No.223B2306)the Innovation Capability Support Program of Shaanxi Province(2023-CX-TD-49)the Natural Science Basic Research Program of Shaanxi Province(2025JC-JCQN-043).
文摘The rovibrational spectra of thioanisole(TA)and its halogenated derivatives,3-fluorothioanisole(3FTA)and 3-chlorothioanisole(3ClTA),were measured using synchrotron-based Fourier transform infrared spectroscopy(FTIR)at the Canadian Light Source.Combined with density functional theory calculations,the stable structures and vibrational modes of TA,3FTA,and 3ClTA in their vibrational states were analyzed.The theoretical vibrational mode frequencies were corrected by simulating the rotational structure of a vibrational band.The contributions of the cis-and trans-isomers of 3FTA and 3ClTA to the FTIR spectra at 298 K were estimated using the Boltzmann distribution,revealing their coexistence in the experimental spectra.The results indicate that both fluorine and chlorine substitution significantly affect the vibrational modes,particularly in the benzene ring.Compared to TA,the FTIR spectra of 3FTA and 3ClTA show changes in the frequencies and intensities of some vibrational modes,with halogen substitution causing specific modes to shift to higher wavenumbers.A comparison of the FTIR spectra of TA,3FTA,and 3ClTA highlights the influence of halogen substitution on vibrational properties,emphasizing how the type and position of the substituent affect frequency shifts and spectral intensities.These findings provide deeper insights into how halogenation alters vibrational spectra,which is crucial for further spectral analysis and molecular structure determination.
文摘Self Assembled Monolayers(SAMs) of a series of mercapto contained azobenzene derivatives with the structure of C n H 2 n +1 AzoO(CH 2) m SH (where n =4,6,8,10,12; with m =3,5 respectively) were prepared and characterized.Wettability measurement of water on the SAMs demonstrates that molecular packing density in the monolayers increases while the alkyl chain in the molecules is lengthened. Both the n and m values have similar contribution to the wetting property of SAMs. The RA IR spectra reveal that the alkyl chains in the SAMs tilt away dramatically from the surface normal direction with the increase in their length. However, the orientation of azobenzene moiety is found to be influenced slightly by the alkyl chain length, which is due to the tenderness of the molecule.
基金supported by the National Natural Science Foundation of China(No.21101085)the Natural Science Foundation of Liaoning Province(No.2015020196)+2 种基金the Fushun Science&Technology Program(No.FSKJHT 201423)the Liaoning Excellent Talents Program in University(No.LJQ2012031)the Talent Scientific Research Fund of Liaoning Shihua University(No.2016XJJ-006)~~
