The molecular geometries, frontier molecular orbital properties, and absorption and emission properties of three 4-phenoxy-1,8-naphthalimide derivatives, namely 4-phenoxy-N-（2-hydroxyethyl）-1,8-naphthalimide（1）,4-...The molecular geometries, frontier molecular orbital properties, and absorption and emission properties of three 4-phenoxy-1,8-naphthalimide derivatives, namely 4-phenoxy-N-（2-hydroxyethyl）-1,8-naphthalimide（1）,4-（2-tert-butylphenoxy）-N-（2-hydroxyethyl）-1,8-naphthalimide（2）, and 4-[2,4-di（tert-butyl）]phenoxy-N-（2-hydroxyethyl）-1,8-naphthalimide（3）, are investigated by density functional theory（DFT） and time-dependent density functional theory（TD-DFT） calculations in conjunction with polarizable continuum models（PCMs）. Four functionals and ten basis sets are employed for 1 to calculate the electron transition energies, which were compared with the experimental observations. Our results reveal that the B3LYP/6-311＋G（d,p） method is the best choice to reproduce the experimental spectra. Moreover, the effects of substituents on the molecular geometries, electronic structures, absorption and emission spectra are also studied at the B3LYP/6-311＋G（d,p） level. We find that the gap between the highest occupied molecular orbital（HOMO） and the lowest unoccupied molecular orbital（LUMO） decreases with increasing the number of tert-butyl substituents onto the phenoxy groups, suggesting red-shift of the absorption and emission bands. This is related to the increase of conjugation from 1 to 2 and 3. Our calculations are in good agreement with the experimental results.展开更多
Two 1,8-naphthalimide derivatives of 7H-benzimidazo[2,1,-a]benz[de] isoquino- lin-7-one（1） and 4-bromo-7H-benzimidazo[2,1,-a]benz[de]isoquinolin-7-one（2） have been synthesized and characterized by elemental analys...Two 1,8-naphthalimide derivatives of 7H-benzimidazo[2,1,-a]benz[de] isoquino- lin-7-one（1） and 4-bromo-7H-benzimidazo[2,1,-a]benz[de]isoquinolin-7-one（2） have been synthesized and characterized by elemental analysis, IR, 1H NMR, UV-Vis and fluorescence spectra. For the two compounds, density functional theory（DFT） calculations of the structures and natural population atomic charge analysis have been performed at the B3LYP/6-311G＊＊ level of theory. Based on Onsager reaction filed model and by using TD-DFT method at the B3LYP/6-311G＊＊ level, electron spectra of 1 and 2 with solvent effect in CHCl3 solvent have been predicted, which are in agreement with the experimental ones. Comparative studies on 1 and 2 indicate that introducing an electron-withdrawing group of Br into the 4-position of naphthalene ring in 2 does not significantly make the molecular geometry of 2 different from that of 1, but evidently changes the atomic charge redistribution, moves the positive-negative charges center and then changes the dipole moment in 2. Additionally, for compound 2, the existence of Br atom has also influenced the peak intensity and peak locations in both electron and fluorescence spectra.展开更多
Two fluorosensor systems have been designed and synthesized with their photophysical properties and fluorescence responses toward the transition metal ions studied. The fluorosensor was composed of 1,8-naphthalimide a...Two fluorosensor systems have been designed and synthesized with their photophysical properties and fluorescence responses toward the transition metal ions studied. The fluorosensor was composed of 1,8-naphthalimide and 4-chloro-1,8-naphthalimide as fluorophore respectively, an amino moiety as the receptor and a hydrocarbon chain as the spacer to link the fluorophore and receptor. Fluorescence intensity of these systems is very weak due to the process of the efficient intramolecular photoinduced electron transfer （PET） in the absence of metal ions. Titration of the transition metal ions can switch on the fluorescence immediately. The intensity of released fluorescence is even higher than the expected from the consideration of the PET in these systems. It may be rationalized that the receptor bound to transition metal ions and the solvation of the fluorophore by the water molecules from the hydrated transition metal salts, may significantly cause fluorescence enhancement.展开更多
The halogen as a kind of alkylating reagent is used to introduce new group to realize the fluorescence sensors efficient of metal ion detection. The substituent at C-4 position was double bromine, which defined that t...The halogen as a kind of alkylating reagent is used to introduce new group to realize the fluorescence sensors efficient of metal ion detection. The substituent at C-4 position was double bromine, which defined that the halogen as an alkylating reagent should be further researched and detected for Hg2＋. Therefore, the N-n-butyl-4-[di（bromoethyl）]amino-1,8-naphthalimide has been synthesized to detect some metal ions. The title compound has been prepared via substitute reaction and was characterized by IR, 1H NMR, 13 C NMR, and MS. It crystallizes in triclinic, space group P1 with a = 9.0071（18）, b = 9.804（2）, c = 13.073（3）A, α = 73.17（3）, β = 71.73（3）, γ = 62.95（3）°, Z = 2, V = 961.5（3） A3, Dc = 1.666 g/cm3, F（000） = 484, μ（Mo Kα） = 4.232 mm-1, R = 0.0429 and w R = 0.1004. The presence of intermolecular hydrogen bonds as well as π-π stacking interaction led to the stability of the compound. The fluorescence intensity was obviously lower than that of other ions when Hg2＋ was added with the concentration of 1 × 10^-5 mol·L-1.展开更多
The ligand of N-（2-hydroxybenzylideneamino）-1,8-naphthalimide （HL） and its metal complexes of CuL2 （1） and CoL2 （2） have been synthesized. Elemental analysis, IR and X-ray single-crystal diffraction characteri...The ligand of N-（2-hydroxybenzylideneamino）-1,8-naphthalimide （HL） and its metal complexes of CuL2 （1） and CoL2 （2） have been synthesized. Elemental analysis, IR and X-ray single-crystal diffraction characterizations for 1 and 2 have been carried out. In the complexes of 1 and 2, the central metallic ions of Cu^2＋ and Co^2＋ coordinate with two deprotonated ligands of L-, respectively and adopt distorted square planar geometries. The thermal analysis result shows that the two complexes undergo two similar decomposition processes because of their similar geometric configurations. For the two complexes, fluorescence spectra measurements indicate that complex CoL2 emits stronger blue fluorescence than HL and the complex CuL2 does not emit fluorescence at all.展开更多
Membrane permeability and intracellular diffusion of fluorescent probes determine staining selectivity of intracellular substructures.However,the relationship between the molecular structure of fluorescent probes and ...Membrane permeability and intracellular diffusion of fluorescent probes determine staining selectivity of intracellular substructures.However,the relationship between the molecular structure of fluorescent probes and their membrane permeability and intracellular distribution is poorly understood.In this paper,we reported a series of 1,8-naphthalimide dyes and carried out cell imaging experiments,and found that the presence of amino hydrogen in these dyes played a crucial role in their cell membrane permeability and intracellular distribution.The secondary amino group containing compounds 1-4 show excellent membrane permeability and strong fluorescence in living cells.While the tertiary amine containing dyes 5 and 6 can hardly permeate the cell membrane though they show extremely similar structure with compounds 2-4.Compound 1 can selectively image lipid droplets by selecting the wavelength of excitation light.With the specificity for lysosomes,2 and 4 have been used in long-term time-lapses imaging of lysosomal dynamics and tracking the process of lysosome-lysosome interaction,fusion and movement.The effect of hydrogen-containing amino substituent on the cell membrane permeability of fluorescent molecules is promising for the development of better biocompatible probes.展开更多
3-Hydroxy-4-chloro-1,8-naphthalic anhydride has been designed and solvent-free synthesized with 1,8-naphthalic anhydride as starting material under microwave irradiation conditions.The result compound has been charact...3-Hydroxy-4-chloro-1,8-naphthalic anhydride has been designed and solvent-free synthesized with 1,8-naphthalic anhydride as starting material under microwave irradiation conditions.The result compound has been characterized by 1H NMR,MS and Elemental analysis.All reactive steps have been optimized,good reproducibility and high yield(total yield is 64%)have been obtained.When 3-Hydroxy-4-chloro-1,8-naphthalic anhydride is radiated by ultraviolet light at 249 nm,it emits intensive blue fluorescence.3-Hydroxy-4-chloro-1,8-naphthalic anhydride would be a potential materials for many blue fluorescent organic materials.展开更多
基金supported by the Scientific Research Fund of Hubei Provincial Education Department(No.Q20122909)the Open Fund of Key Laboratory of Biologic Resources Protection and Utilization of Hubei Province(No.PKLHB1314)the First-class Discipline of Forestry in Hubei Minzu University
文摘The molecular geometries, frontier molecular orbital properties, and absorption and emission properties of three 4-phenoxy-1,8-naphthalimide derivatives, namely 4-phenoxy-N-（2-hydroxyethyl）-1,8-naphthalimide（1）,4-（2-tert-butylphenoxy）-N-（2-hydroxyethyl）-1,8-naphthalimide（2）, and 4-[2,4-di（tert-butyl）]phenoxy-N-（2-hydroxyethyl）-1,8-naphthalimide（3）, are investigated by density functional theory（DFT） and time-dependent density functional theory（TD-DFT） calculations in conjunction with polarizable continuum models（PCMs）. Four functionals and ten basis sets are employed for 1 to calculate the electron transition energies, which were compared with the experimental observations. Our results reveal that the B3LYP/6-311＋G（d,p） method is the best choice to reproduce the experimental spectra. Moreover, the effects of substituents on the molecular geometries, electronic structures, absorption and emission spectra are also studied at the B3LYP/6-311＋G（d,p） level. We find that the gap between the highest occupied molecular orbital（HOMO） and the lowest unoccupied molecular orbital（LUMO） decreases with increasing the number of tert-butyl substituents onto the phenoxy groups, suggesting red-shift of the absorption and emission bands. This is related to the increase of conjugation from 1 to 2 and 3. Our calculations are in good agreement with the experimental results.
基金Supported by Doctor Foundation of Shandong Province(No.BS2010CL021)Natural Science Foundation of Shandong Province(ZR2009AL020)Jiangsu Key Laboratory for Chemistry of Low-dimensional Materials P.R.China(JSKC12106 and JSKC12107)
文摘Two 1,8-naphthalimide derivatives of 7H-benzimidazo[2,1,-a]benz[de] isoquino- lin-7-one（1） and 4-bromo-7H-benzimidazo[2,1,-a]benz[de]isoquinolin-7-one（2） have been synthesized and characterized by elemental analysis, IR, 1H NMR, UV-Vis and fluorescence spectra. For the two compounds, density functional theory（DFT） calculations of the structures and natural population atomic charge analysis have been performed at the B3LYP/6-311G＊＊ level of theory. Based on Onsager reaction filed model and by using TD-DFT method at the B3LYP/6-311G＊＊ level, electron spectra of 1 and 2 with solvent effect in CHCl3 solvent have been predicted, which are in agreement with the experimental ones. Comparative studies on 1 and 2 indicate that introducing an electron-withdrawing group of Br into the 4-position of naphthalene ring in 2 does not significantly make the molecular geometry of 2 different from that of 1, but evidently changes the atomic charge redistribution, moves the positive-negative charges center and then changes the dipole moment in 2. Additionally, for compound 2, the existence of Br atom has also influenced the peak intensity and peak locations in both electron and fluorescence spectra.
基金Project supported by the National Natural Science Foundation of China （Nos. 20332020.20472079）. Dedicated to Professor Xikui Jiang on the occasion of his 80th birthday.
文摘Two fluorosensor systems have been designed and synthesized with their photophysical properties and fluorescence responses toward the transition metal ions studied. The fluorosensor was composed of 1,8-naphthalimide and 4-chloro-1,8-naphthalimide as fluorophore respectively, an amino moiety as the receptor and a hydrocarbon chain as the spacer to link the fluorophore and receptor. Fluorescence intensity of these systems is very weak due to the process of the efficient intramolecular photoinduced electron transfer （PET） in the absence of metal ions. Titration of the transition metal ions can switch on the fluorescence immediately. The intensity of released fluorescence is even higher than the expected from the consideration of the PET in these systems. It may be rationalized that the receptor bound to transition metal ions and the solvation of the fluorophore by the water molecules from the hydrated transition metal salts, may significantly cause fluorescence enhancement.
基金supported by the National Natural Science Foundation of China(No.31572042)the Research Science Foundation in Technology Innovation of Harbin(No.2015RAYXJ010)
文摘The halogen as a kind of alkylating reagent is used to introduce new group to realize the fluorescence sensors efficient of metal ion detection. The substituent at C-4 position was double bromine, which defined that the halogen as an alkylating reagent should be further researched and detected for Hg2＋. Therefore, the N-n-butyl-4-[di（bromoethyl）]amino-1,8-naphthalimide has been synthesized to detect some metal ions. The title compound has been prepared via substitute reaction and was characterized by IR, 1H NMR, 13 C NMR, and MS. It crystallizes in triclinic, space group P1 with a = 9.0071（18）, b = 9.804（2）, c = 13.073（3）A, α = 73.17（3）, β = 71.73（3）, γ = 62.95（3）°, Z = 2, V = 961.5（3） A3, Dc = 1.666 g/cm3, F（000） = 484, μ（Mo Kα） = 4.232 mm-1, R = 0.0429 and w R = 0.1004. The presence of intermolecular hydrogen bonds as well as π-π stacking interaction led to the stability of the compound. The fluorescence intensity was obviously lower than that of other ions when Hg2＋ was added with the concentration of 1 × 10^-5 mol·L-1.
基金supported by the Fund of Jiangsu Key Laboratory for Chemistry of Low-dimensional Materials (JSKC08047)Fund of Huanyin Teachers College (08HSJSK003)
文摘The ligand of N-（2-hydroxybenzylideneamino）-1,8-naphthalimide （HL） and its metal complexes of CuL2 （1） and CoL2 （2） have been synthesized. Elemental analysis, IR and X-ray single-crystal diffraction characterizations for 1 and 2 have been carried out. In the complexes of 1 and 2, the central metallic ions of Cu^2＋ and Co^2＋ coordinate with two deprotonated ligands of L-, respectively and adopt distorted square planar geometries. The thermal analysis result shows that the two complexes undergo two similar decomposition processes because of their similar geometric configurations. For the two complexes, fluorescence spectra measurements indicate that complex CoL2 emits stronger blue fluorescence than HL and the complex CuL2 does not emit fluorescence at all.
基金supported by the National Natural Science Foundation of China(Nos.22278394,22078314 and 21908216)Dalian Institute of Chemical Physics(Nos.DICPI202227 and DICPI202142).
文摘Membrane permeability and intracellular diffusion of fluorescent probes determine staining selectivity of intracellular substructures.However,the relationship between the molecular structure of fluorescent probes and their membrane permeability and intracellular distribution is poorly understood.In this paper,we reported a series of 1,8-naphthalimide dyes and carried out cell imaging experiments,and found that the presence of amino hydrogen in these dyes played a crucial role in their cell membrane permeability and intracellular distribution.The secondary amino group containing compounds 1-4 show excellent membrane permeability and strong fluorescence in living cells.While the tertiary amine containing dyes 5 and 6 can hardly permeate the cell membrane though they show extremely similar structure with compounds 2-4.Compound 1 can selectively image lipid droplets by selecting the wavelength of excitation light.With the specificity for lysosomes,2 and 4 have been used in long-term time-lapses imaging of lysosomal dynamics and tracking the process of lysosome-lysosome interaction,fusion and movement.The effect of hydrogen-containing amino substituent on the cell membrane permeability of fluorescent molecules is promising for the development of better biocompatible probes.
文摘3-Hydroxy-4-chloro-1,8-naphthalic anhydride has been designed and solvent-free synthesized with 1,8-naphthalic anhydride as starting material under microwave irradiation conditions.The result compound has been characterized by 1H NMR,MS and Elemental analysis.All reactive steps have been optimized,good reproducibility and high yield(total yield is 64%)have been obtained.When 3-Hydroxy-4-chloro-1,8-naphthalic anhydride is radiated by ultraviolet light at 249 nm,it emits intensive blue fluorescence.3-Hydroxy-4-chloro-1,8-naphthalic anhydride would be a potential materials for many blue fluorescent organic materials.
