The excited state intramolecular proton transfer of four derivatives(FM, BFM, BFBC, CCM) of 3-hydroxychromone is investigated.The geometries of different substituents are optimized to study the substituent effects on ...The excited state intramolecular proton transfer of four derivatives(FM, BFM, BFBC, CCM) of 3-hydroxychromone is investigated.The geometries of different substituents are optimized to study the substituent effects on proton transfer.The mechanism of hydrogen bond enhancement is qualitatively elucidated by comparing the infrared spectra, the reduced density gradient, and the frontier molecular orbitals.The calculated electronic spectra are consistent with the experimental results.To quantify the proton transfer, the potential energy curves(PECs) of the four derivatives in S0 and S1 states are scanned.It is concluded that the ability of proton transfer follows the order: FM > BFM > BFBC > CCM.展开更多
Mechanochromic polymers based on non-covalent changes have attracted much attention recently.Herein,we report the impact of inter/intramolecular hydrogen bonds on polymer mechanochromism from the excited state intramo...Mechanochromic polymers based on non-covalent changes have attracted much attention recently.Herein,we report the impact of inter/intramolecular hydrogen bonds on polymer mechanochromism from the excited state intramolecular proton transfer (ESIPT) process.PhMz-NH2-OH and PhMz=2A are designed and obtained by simple and high-yield synthesis,and are connected into polyurethane and poly(methyl acrylate-co-2-ethylhexyl acrylate),respectively.In the initial state,the PhMz-NH2-OH@PU sample shows blue fluorescence from the excited enol form (E*) excitons,owing to intermolecular hydrogen bonds that interrupt the ESIPT reactions but the PhMz=2A@PMA-2-EA sample expresses cyan fluorescence belonging to the excited keto form (K*) emission,implying that the intramolecular hydrogen bonds matter.Furthermore,under stretching,external force can tune the emission of the PhMz=2A@PMA-2-EA sample from K* to E* state.Though external force can putatively still promote a bond rotation,ESIPT reactions remain equivalently interrupted in both the relaxed and stressed states in a hydrogen-bond donating environment.DFT calculation confirms the force-induced increase in dihedral angle for the transition of ESIPT-on/off.Thus,PhMz-NH2-OH@PU and PhMz=2A@PMA-2-EA showed disparate initial ESIPT states and further different responses/sensitivity to force.This study reports a novel and efficient strategy for enriching mechanochromic investigation and extending the applications of ESIPT reactions.展开更多
Graphene quantum dots(GQDs)have attracted increasing attention due to their favorable optical properties and have been widely used,e.g.,in the biomedical field.However,the properties related to the chemical structure ...Graphene quantum dots(GQDs)have attracted increasing attention due to their favorable optical properties and have been widely used,e.g.,in the biomedical field.However,the properties related to the chemical structure of GQDs,resulting in solventdependent optical properties,still remain unclear.Herein,we present the synthesis of long-wavelength emitting GQDs with a size of about 3.6 nm via a solvothermal method using oxo-functionalized graphene(oxo-G)and p-phenylenediamine as precursors and their structural and surface chemical analysis by transmission electron and atomic force microscopy(TEM;AFM)as well as Fourier-transform infrared,Raman,and X-ray photoelectron spectroscopy(FTIR;Raman;XPS).Subsequently,the influence of solvent polarity and proticity on the optical properties of the as-prepared GQDs bearing–OH,–NH_(2),–COOH and pyridine surface groups was investigated.Based on the results of the absorption and fluorescence(FL)studies,a possible luminescence mechanism is proposed.The observed solvent-induced changes in the spectral position of the FL maximum,FL quantum yield,and FL decay kinetics in protic and aprotic solvents of low and high polarity are ascribed to a combination of polarity effects,intramolecular charge transfer(ICT)processes,and hydrogen bonding.Moreover,the potential of GQDs for the optical sensing of trace amount of water was assessed.The results of our systematic spectroscopic study will promote the rational design of GQDs and shed more light on the FL mechanism of carbon-based fluorescent nanomaterials.展开更多
Excited-state intramolecular proton transfer(ESIPT) molecules are broadly applied to UV absorbers, fluorescence sensing, and lighting materials. In previous work, the fluorescence colors of oxazoline-substituted hydro...Excited-state intramolecular proton transfer(ESIPT) molecules are broadly applied to UV absorbers, fluorescence sensing, and lighting materials. In previous work, the fluorescence colors of oxazoline-substituted hydroxyfluorenes and hydroxylated benzoxazole were diversified by adding the π-conjugation. There is intriguing that the mechanism of diversified fluorescence colors induced by ESIPT. Here, the density functional theory(DFT) and time-dependent DFT(TDDFT)are advised to identify the effects of π-conjugation on ESIPT and photophysical properties. The stabilized geometrical configurations, frontier molecular orbitals(FMOs) isosurfaces, and O–H stretching vibration frequency analysis demonstrate that PT processes are more active in S1state. Constructing the minimum energy pathways of ESIPT processes, we find that the calculated peak of enol and keto fluorescence of naphthoxazole(NO–OH) is distinctly bathochromic-shift relative to the oxazoline-substituted hydroxyfluorenes(Oxa–OH) configuration when adding π-conjugation-substitution, and it means that π-conjugation-substitution can diversify the fluorescence color. We hope our studies can establish new channels to devise the ESIPT-based molecules.展开更多
The ground- and excited-state intramolecular proton transfer processes of 2-（2-R （R=OH, NH2, SH） phenyl （or pyridyl）） benzoxazoles （or benzothiazoles） are investigated by the DFT methods. The calculated result...The ground- and excited-state intramolecular proton transfer processes of 2-（2-R （R=OH, NH2, SH） phenyl （or pyridyl）） benzoxazoles （or benzothiazoles） are investigated by the DFT methods. The calculated results indicate that in the ground state there is a high correlation （R=0.9950） between the proton transfer barrier and the intramolecular hydrogen bonds （IMHB） strength. The increase of the strength of IMHB in the proton transfer processes leads to a larger barrier contributions. Intramolecular proton transfer process pathway is along with the minimal difference of change value in the IMHB angle. In the excited-state, there is a similar relationship between the IMHB and the bartier.展开更多
Intramolecular charge transfer(ICT) dual fluorescence of p-dimethylamino-benzoylhydrazine(DMABH) in acetonitrile was found to show a highly selective response to HSO - 4 over several other anions. The intensity ratio ...Intramolecular charge transfer(ICT) dual fluorescence of p-dimethylamino-benzoylhydrazine(DMABH) in acetonitrile was found to show a highly selective response to HSO - 4 over several other anions. The intensity ratio of the CT to LE emission and the total fluorescence intensity of DMABH decreased with increasing bisulfate concentration. While the dual fluorescence response was very similar to that of DMABA at a low HSO - 4 concentration, the CT intensity decreased drastically and the LE intensity remained almost constant, however, the difference was observed at a high HSO - 4 concentration, in which both the CT and LE intensities of DMABH decreased. A different recognition mechanism from that of DMABA was suggested for DMABH in which hydrogen bonding and protonization were the recognition interactions at low and high HSO - 4 concentrations, respectively.展开更多
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11874241,11847224,and 11804195)the Shandong Province Higher Educational Science and Technology Program,China(Grant No.J15LJ03)+1 种基金the Taishan Scholar Project of Shandong Province,China,China Post-Doctoral Foundation(Grant No.2018M630796)the Natural Science Foundation of Shandong Province,China(Grant No.ZR2018BA034)
文摘The excited state intramolecular proton transfer of four derivatives(FM, BFM, BFBC, CCM) of 3-hydroxychromone is investigated.The geometries of different substituents are optimized to study the substituent effects on proton transfer.The mechanism of hydrogen bond enhancement is qualitatively elucidated by comparing the infrared spectra, the reduced density gradient, and the frontier molecular orbitals.The calculated electronic spectra are consistent with the experimental results.To quantify the proton transfer, the potential energy curves(PECs) of the four derivatives in S0 and S1 states are scanned.It is concluded that the ability of proton transfer follows the order: FM > BFM > BFBC > CCM.
基金supported by the National Natural Science Foundationof China(22175015,21704002 and 22375013)the Beijing Natural Science Foundation(2182054)+1 种基金the Big Science Project from BUCT(XK180301)the Fundamental Research Funds forthe Central Universities to Z.Y.M.
文摘Mechanochromic polymers based on non-covalent changes have attracted much attention recently.Herein,we report the impact of inter/intramolecular hydrogen bonds on polymer mechanochromism from the excited state intramolecular proton transfer (ESIPT) process.PhMz-NH2-OH and PhMz=2A are designed and obtained by simple and high-yield synthesis,and are connected into polyurethane and poly(methyl acrylate-co-2-ethylhexyl acrylate),respectively.In the initial state,the PhMz-NH2-OH@PU sample shows blue fluorescence from the excited enol form (E*) excitons,owing to intermolecular hydrogen bonds that interrupt the ESIPT reactions but the PhMz=2A@PMA-2-EA sample expresses cyan fluorescence belonging to the excited keto form (K*) emission,implying that the intramolecular hydrogen bonds matter.Furthermore,under stretching,external force can tune the emission of the PhMz=2A@PMA-2-EA sample from K* to E* state.Though external force can putatively still promote a bond rotation,ESIPT reactions remain equivalently interrupted in both the relaxed and stressed states in a hydrogen-bond donating environment.DFT calculation confirms the force-induced increase in dihedral angle for the transition of ESIPT-on/off.Thus,PhMz-NH2-OH@PU and PhMz=2A@PMA-2-EA showed disparate initial ESIPT states and further different responses/sensitivity to force.This study reports a novel and efficient strategy for enriching mechanochromic investigation and extending the applications of ESIPT reactions.
基金This research is supported by the Deutsche Forschungsgemeinschaft project No.392444269(DFG,German Research Foundation),the China Scholarship Council(CSC)supported by the DFG.C.N.and A.T.acknowledge DFG financial support via the research infrastructure grant INST 275/257-1 FUGG(project No.313713174)+2 种基金funding through ESF Research Groups 2019 FGR 0080“ESTI”and 2020 FGR 0051“GraphSens”as well as BMWi project ZF4817401VS9“TDraCon”Z.H.from Soochow University is acknowledged for conducting TEM measurements.U.R.G and L.S.gratefully acknowledge financial support by the European Metrology Programme for Innovation and Research(EMPIR)as part of the projects 18HLT02“AeroTox”The EMPIR initiative is co-funded by the European Union’s Horizon 2020 research and innovation programme and by the EMPIR participating states.
文摘Graphene quantum dots(GQDs)have attracted increasing attention due to their favorable optical properties and have been widely used,e.g.,in the biomedical field.However,the properties related to the chemical structure of GQDs,resulting in solventdependent optical properties,still remain unclear.Herein,we present the synthesis of long-wavelength emitting GQDs with a size of about 3.6 nm via a solvothermal method using oxo-functionalized graphene(oxo-G)and p-phenylenediamine as precursors and their structural and surface chemical analysis by transmission electron and atomic force microscopy(TEM;AFM)as well as Fourier-transform infrared,Raman,and X-ray photoelectron spectroscopy(FTIR;Raman;XPS).Subsequently,the influence of solvent polarity and proticity on the optical properties of the as-prepared GQDs bearing–OH,–NH_(2),–COOH and pyridine surface groups was investigated.Based on the results of the absorption and fluorescence(FL)studies,a possible luminescence mechanism is proposed.The observed solvent-induced changes in the spectral position of the FL maximum,FL quantum yield,and FL decay kinetics in protic and aprotic solvents of low and high polarity are ascribed to a combination of polarity effects,intramolecular charge transfer(ICT)processes,and hydrogen bonding.Moreover,the potential of GQDs for the optical sensing of trace amount of water was assessed.The results of our systematic spectroscopic study will promote the rational design of GQDs and shed more light on the FL mechanism of carbon-based fluorescent nanomaterials.
基金supported by the National Natural Science Foundation of China (Grant No. 11974152)the Shenyang High level Innovative Talents Program (Grant No. RC200565)+1 种基金the Science program of Liaoning Provincial Department of Education (Grant No. LJKZ0097)the Intercollegiate cooperation project of colleges and universities of Liaoning Provincial Department of Education。
文摘Excited-state intramolecular proton transfer(ESIPT) molecules are broadly applied to UV absorbers, fluorescence sensing, and lighting materials. In previous work, the fluorescence colors of oxazoline-substituted hydroxyfluorenes and hydroxylated benzoxazole were diversified by adding the π-conjugation. There is intriguing that the mechanism of diversified fluorescence colors induced by ESIPT. Here, the density functional theory(DFT) and time-dependent DFT(TDDFT)are advised to identify the effects of π-conjugation on ESIPT and photophysical properties. The stabilized geometrical configurations, frontier molecular orbitals(FMOs) isosurfaces, and O–H stretching vibration frequency analysis demonstrate that PT processes are more active in S1state. Constructing the minimum energy pathways of ESIPT processes, we find that the calculated peak of enol and keto fluorescence of naphthoxazole(NO–OH) is distinctly bathochromic-shift relative to the oxazoline-substituted hydroxyfluorenes(Oxa–OH) configuration when adding π-conjugation-substitution, and it means that π-conjugation-substitution can diversify the fluorescence color. We hope our studies can establish new channels to devise the ESIPT-based molecules.
基金Project supported by the National Natural Science Foundation of China （Nos. 20772027, 20803020, 20971041） and the Scientific Research Fund of Hunan Provincial Education Department （Nos. 08C342,10J J4011, 09K081, 09B032）.
文摘The ground- and excited-state intramolecular proton transfer processes of 2-（2-R （R=OH, NH2, SH） phenyl （or pyridyl）） benzoxazoles （or benzothiazoles） are investigated by the DFT methods. The calculated results indicate that in the ground state there is a high correlation （R=0.9950） between the proton transfer barrier and the intramolecular hydrogen bonds （IMHB） strength. The increase of the strength of IMHB in the proton transfer processes leads to a larger barrier contributions. Intramolecular proton transfer process pathway is along with the minimal difference of change value in the IMHB angle. In the excited-state, there is a similar relationship between the IMHB and the bartier.
文摘Intramolecular charge transfer(ICT) dual fluorescence of p-dimethylamino-benzoylhydrazine(DMABH) in acetonitrile was found to show a highly selective response to HSO - 4 over several other anions. The intensity ratio of the CT to LE emission and the total fluorescence intensity of DMABH decreased with increasing bisulfate concentration. While the dual fluorescence response was very similar to that of DMABA at a low HSO - 4 concentration, the CT intensity decreased drastically and the LE intensity remained almost constant, however, the difference was observed at a high HSO - 4 concentration, in which both the CT and LE intensities of DMABH decreased. A different recognition mechanism from that of DMABA was suggested for DMABH in which hydrogen bonding and protonization were the recognition interactions at low and high HSO - 4 concentrations, respectively.
