UV-Vis spectrum and the third-order nonlinear optical properties of the chiral camphor-derived β-diketonate have been studied at the B3LYP/6-31G＊ level. The results showed that the introduction of electron-drawing g...UV-Vis spectrum and the third-order nonlinear optical properties of the chiral camphor-derived β-diketonate have been studied at the B3LYP/6-31G＊ level. The results showed that the introduction of electron-drawing group -CF3 and -C3F7 on β-diketonate made the strongest absorption peak red-shift and the lowest energy absorption blue-shied. Introduction of -OC2H5 on the benzene or pyridine ring made the lowest energy absorption blue-shift. When the -C2H3 was introduced on the benzene or pyridine ring, the lowest energy absorption was red-shifted. Introduction of electron-donating group on β-diketonate can enlarge their nonlinear optical properties. On the contrary, the introduction of electron-drawing group dropped it down.展开更多
In this study,twenty disazo reactive red dyes with J acid as coupling components were selected,and their ground state geometry were studied with BLYP functional and TZVP basis set. The UV-vis absorption spectra were c...In this study,twenty disazo reactive red dyes with J acid as coupling components were selected,and their ground state geometry were studied with BLYP functional and TZVP basis set. The UV-vis absorption spectra were calculated by time-dependent density functional theory（TDDFT） employing B3 LYP and PBE0 hybrid functionals and TZVP basis set,and the absolute mean errors are 0.094 e V and 0.133 e V for B3 LYP and PBE0,respectively. From the comparison of the calculated λ_（max） of the three conformations of disazo reactive red dye,cis-,trans-,and azo,with that of experimental one,we find out that conformation plays an important role on UV-Vis absorption. Dyes 6 and 8 exist in azo conformation rather than in cis-conformation. ＂Hole-electron＂ distribution analysis reveals that although these λ_（max） arises from different electron transitions,these electron excitations have the same character of local excitation（LE）.展开更多
Size-controlled flow synthesis of nanoporous particles are of considerable interest for future industrial applications,however,is facing challenges due to lack of in-situ method for size-characterization in fluidic en...Size-controlled flow synthesis of nanoporous particles are of considerable interest for future industrial applications,however,is facing challenges due to lack of in-situ method for size-characterization in fluidic environment.We present that ultraviolet-visible(UV-vis)absorption spectroscopy can be integrated into a flow-synthesis system which was produced by femtosecond laser micro machining.The shift of the absorption peak position of the ex-situ and in-situ UV-vis spectra correlates to variation of size of porous metal-organic frameworks crystals.ZIF-67 crystals with a size in the range from 200 nm to1025 nm are fabricated with the assistance of tri-ethylamine under monitoring of in-situ UV-vis spectra.The ZIF-67 crystals are converted into nanoporous carbons particles with controlled sizes.These materials show size-dependent performance in Na-ion battery and size-independent performance in metal/H_(2)O seawater battery.展开更多
The aggregation of meso-tetrakis(4-hydroxyphenyl)porphyrin (H2THPP) in dimethyl- formamide (DMF)-water solution and in DMF-chloroform solution was studied by UV-vis absorption spectroscopy. The red shift of Soret ba...The aggregation of meso-tetrakis(4-hydroxyphenyl)porphyrin (H2THPP) in dimethyl- formamide (DMF)-water solution and in DMF-chloroform solution was studied by UV-vis absorption spectroscopy. The red shift of Soret band indicates the formation of J-type aggregates of H2THPP in these two solutions. However, different shift extent of Soret band, 12 nm in DMF-water solution and 32 nm in DMF-chloroform solution, implies structural difference between these two J-type aggregates. The hydrogen bond between hydroxyl group and N-H bonds in porphyrin ring is thought as the main cause to the formation of J-type aggregate in DMF- chloroform solution, whereas the π?σ interaction between two adjacent porphyrin cores is thought as the main cause of the formation of J-type aggregate in DMF-water solution展开更多
合成了两类长链烷基二茂铁取代的卟啉及其金属锌卟啉,其中一类二茂铁通过酰胺键与卟啉相连,长链在外围（卟啉5与锌卟啉6）;另一类二茂铁通过长链与卟啉相连（卟啉7与锌卟啉8）.研究了两类卟啉及其金属锌卟啉的光谱与电化学性质.两类卟...合成了两类长链烷基二茂铁取代的卟啉及其金属锌卟啉,其中一类二茂铁通过酰胺键与卟啉相连,长链在外围（卟啉5与锌卟啉6）;另一类二茂铁通过长链与卟啉相连（卟啉7与锌卟啉8）.研究了两类卟啉及其金属锌卟啉的光谱与电化学性质.两类卟啉配体的吸收位置几乎相同,与卟啉配体相比,两类金属锌卟啉的最大吸收均收发生了7 nm的红移.荧光光谱中,酰胺键桥连的卟啉5与锌卟啉6的荧光猝灭程度相对增大,量子产率降低.电化学研究表明,当卟啉配体与金属锌离子配位后,卟啉环及二茂铁的氧化还原半波电位均发生负移.此外,将连接二茂铁与卟啉的酰胺键换成长链烷基后,卟啉配体及配合物的第一氧化电势略有降低（13~18 m V）,而二茂铁的第一氧化电势却降低182~194m V左右.展开更多
基金supported by the National Natural Science Foundation of China(21172161)
文摘UV-Vis spectrum and the third-order nonlinear optical properties of the chiral camphor-derived β-diketonate have been studied at the B3LYP/6-31G＊ level. The results showed that the introduction of electron-drawing group -CF3 and -C3F7 on β-diketonate made the strongest absorption peak red-shift and the lowest energy absorption blue-shied. Introduction of -OC2H5 on the benzene or pyridine ring made the lowest energy absorption blue-shift. When the -C2H3 was introduced on the benzene or pyridine ring, the lowest energy absorption was red-shifted. Introduction of electron-donating group on β-diketonate can enlarge their nonlinear optical properties. On the contrary, the introduction of electron-drawing group dropped it down.
基金Supported by the Natural Science Foundation of Hubei Province(2010CDA089)the Foundation of Hubei Provincial Education Department(D20131605)the Discipline Innovation Team Project of Wuhan Textile University(201401020)
文摘In this study,twenty disazo reactive red dyes with J acid as coupling components were selected,and their ground state geometry were studied with BLYP functional and TZVP basis set. The UV-vis absorption spectra were calculated by time-dependent density functional theory（TDDFT） employing B3 LYP and PBE0 hybrid functionals and TZVP basis set,and the absolute mean errors are 0.094 e V and 0.133 e V for B3 LYP and PBE0,respectively. From the comparison of the calculated λ_（max） of the three conformations of disazo reactive red dye,cis-,trans-,and azo,with that of experimental one,we find out that conformation plays an important role on UV-Vis absorption. Dyes 6 and 8 exist in azo conformation rather than in cis-conformation. ＂Hole-electron＂ distribution analysis reveals that although these λ_（max） arises from different electron transitions,these electron excitations have the same character of local excitation（LE）.
基金supported by National Natural Science Foundation of China(Nos.11674340,21473059)Key Project of the Shanghai Science and Technology Committee(No.18DZ1112700)。
文摘Size-controlled flow synthesis of nanoporous particles are of considerable interest for future industrial applications,however,is facing challenges due to lack of in-situ method for size-characterization in fluidic environment.We present that ultraviolet-visible(UV-vis)absorption spectroscopy can be integrated into a flow-synthesis system which was produced by femtosecond laser micro machining.The shift of the absorption peak position of the ex-situ and in-situ UV-vis spectra correlates to variation of size of porous metal-organic frameworks crystals.ZIF-67 crystals with a size in the range from 200 nm to1025 nm are fabricated with the assistance of tri-ethylamine under monitoring of in-situ UV-vis spectra.The ZIF-67 crystals are converted into nanoporous carbons particles with controlled sizes.These materials show size-dependent performance in Na-ion battery and size-independent performance in metal/H_(2)O seawater battery.
基金supported by the National Natural Science Foundation of China(Grant No.20303009)
文摘The aggregation of meso-tetrakis(4-hydroxyphenyl)porphyrin (H2THPP) in dimethyl- formamide (DMF)-water solution and in DMF-chloroform solution was studied by UV-vis absorption spectroscopy. The red shift of Soret band indicates the formation of J-type aggregates of H2THPP in these two solutions. However, different shift extent of Soret band, 12 nm in DMF-water solution and 32 nm in DMF-chloroform solution, implies structural difference between these two J-type aggregates. The hydrogen bond between hydroxyl group and N-H bonds in porphyrin ring is thought as the main cause to the formation of J-type aggregate in DMF- chloroform solution, whereas the π?σ interaction between two adjacent porphyrin cores is thought as the main cause of the formation of J-type aggregate in DMF-water solution
文摘合成了两类长链烷基二茂铁取代的卟啉及其金属锌卟啉,其中一类二茂铁通过酰胺键与卟啉相连,长链在外围（卟啉5与锌卟啉6）;另一类二茂铁通过长链与卟啉相连（卟啉7与锌卟啉8）.研究了两类卟啉及其金属锌卟啉的光谱与电化学性质.两类卟啉配体的吸收位置几乎相同,与卟啉配体相比,两类金属锌卟啉的最大吸收均收发生了7 nm的红移.荧光光谱中,酰胺键桥连的卟啉5与锌卟啉6的荧光猝灭程度相对增大,量子产率降低.电化学研究表明,当卟啉配体与金属锌离子配位后,卟啉环及二茂铁的氧化还原半波电位均发生负移.此外,将连接二茂铁与卟啉的酰胺键换成长链烷基后,卟啉配体及配合物的第一氧化电势略有降低（13~18 m V）,而二茂铁的第一氧化电势却降低182~194m V左右.
