[Show abstract][Hide abstract] ABSTRACT: o-hydroxyphenyl-triazine derivatives with formyl substituents were surveyed for the excited state intramolecular proton transfer
(ESIPT). The occurrence of ESIPT was confirmed by well-separated emission bands for the derivatives. A low energy change from
enol to keto in the excited state explains ESIPT for the derivatives.
Chinese Science Bulletin 01/2011; 56(14):1457-1460. · 1.37 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: This paper presents a range of novel new branched conjugated dyes containing benzophenone moiety. As compared with those of 4-(p-benzoyl-styrene)yl-4'-(styrene)yl-triphenylamine (C1) and 4-(p-benzoyl-styrene)yl-4'-3,4,5-trimethoxyl-styrene)yl-triphenylamine (C2), the maximal linear absorption and emission wavelength of 4-(p-benzoyl-styrene)yl-4'-(p'-nitro-styrene)yl-triphenylamine (C3) displays red-shifted remarkably, While the fluorescence quantum yields of C3 are lower than those of C1 and C2 in various solvents. The fluorescence lifetimes of the derivatives were measured, and radiative and non-radiative transition constants of the derivatives were calculated. Two-photon absorption (TPA) optical data of the derivatives were measured by Ti:sapphire femtosecond laser tuning from 720 to 880 nm at intervals of 20 nm. TPA induced fluorescence emission of C3 is red-shifted with respected to that of C1 and C2. TPA cross sections of C3 are larger than those of C1 and C2 in various excited laser frequencies. TPA cross section of C2 and C3 are much larger than those of 3,4,5-(trimethoxylstyrene)yl-triphenylamine (C4) and 4-(p-nitrostyrene)yl-triphenylamine (C5) respectively under various near-IR Ti:sapphire femtosecond laser wavelength. C1 and C2 show similar one- and two- photon optical nature. Geometry optimization with ab initio method confirms that C3 has different electron density distribution, the energy levels in frontier orbitals, the dipole moment changes, the absorption and emission spectroscopy from those of C1 and C2. The cyclic voltammograms of the derivatives were detected in methylene chloride at various scan rates, and the energy of frontier orbials were estimated further from the redox potentials.
Journal of Fluorescence 10/2010; 21(1):393-407. · 1.79 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: This paper presents a variety of conjugated derivatives with different number of arms (4-styryl-triphenylamine: C1, 4,4'-di-styryltriphenylamine: C2, 4,4',4″-tri-styryltriphenylamine: C3). The linear absorption and fluorescence maxima and the molar extinction coefficients are in the order of C1<C2<C3 in various solvents. Two-photon absorption (TPA) up-converted emission of the derivatives were determined with Ti:sapphire femtosecond laser. The maximal TPA emission wavelength and the two-photon absorption cross section of the derivatives are also in the order of C1<C2<C3 in various solvents. The dipole moment changes of the derivatives between the excited state and the ground state were estimated from experiment, and they are in the order of C1<C2<C3, which is confirmed further by the molecular geometry optimization of the derivatives. The electron density distribution and the energy levels of the frontier orbital of the derivatives were analyzed. The cyclic voltammograms of the derivatives were performed and discussed.
Journal of Fluorescence 10/2010; 21(2):545-54. · 1.79 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: This paper presents the investigation of tuning the color and photoluminescence of a range of triphenylamine- based derivatives with various substituent groups. The ultraviolet/visible absorption and fluorescence spectroscopy of the derivatives showed remarkable difference. The molecular geometry optimization demonstrated that the properties of the ground state and the excited state of the compounds have a close relationship with the substituent groups. Therefore, it is possible to tune the color and photoluminescence of the derivatives at molecular level. The cyclic voltammograms of these compounds were detected in methylene chloride at various scan rates. The thermal stabilities of the compounds were analyzed with the different scanning calorimetry and the thermogravimetry.
Chinese Journal of Chemistry 01/2010; 28(6):950-960. · 0.92 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Suitable chemical strategy is a useful approach on the tuning color and photoluminescence of organic dyes. This paper presented tuning novel branched p-nitro-stilbene derivatives efficiently with a new chemical strategy through variation of chemical bridged bond. Linking bonds played significant effects on the absorption and fluorescence spectroscopy of the branched p-nitro-stilbene derivatives. A change from "D-pi-A" to "A-pi-A" chemical structural characteristics occurred for the branched p-nitro-stilbene derivatives as ester bond was attached. This led to not only large hypsochromic shift of the maximal absorption wavelength of the branched p-nitro-stilbene derivatives, but considerable reduction of the fluorescence intensity. While in contrast, the branched p-nitro-stilbene derivatives with ether bond exhibited longer wavelength absorption and much stronger fluorescence emission in modest polar solvent. The cyclic voltammograms of these branched p-nitro-stilbene derivatives were determined. Different electrochemistry processes were observed for the branched p-nitro-stilbene derivatives with various linking bonds. The energies of frontier orbital of the branched p-nitro-stilbene derivatives were estimated from their corresponding redox potentials. Molecular geometry optimization of the branched p-nitro-stilbene derivatives was performed, and the electron density distribution of frontier orbital was analyzed. Thermal stabilities of these branched nitro-stilbene derivatives were investigated via the analysis of the differential scanning calorimetry (DSC) and thermograving (TGA) curves. This paper presented strong evidences that the absorption and fluorescence spectroscopy of the branched stilbene derivatives could be mediated efficiently by chemical strategy.
Journal of Fluorescence 12/2009; 20(1):353-64. · 1.79 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: We discuss the synthesis and characterization of 3',4'-bis(p-benzoylphenylmethoxy)yl-4-nitrostilbene (C1). Ultraviolet and fluorescence spectroscopy was used to investigate its behavior in various solvents. Results showed that the visible absorption of C1 could be assigned to the chromophore and that the attached benzophenone made major contribution to the ultraviolet absorption of C1. This compound exhibited strong fluorescence in modest polar solvents.Acomprehensive investigation of the two-photon properties and electrochemistry of C1 and 2',4'-bis(p-benzoylphenylmethoxy)yl-4-nitrostilbene (C2) was undertaken. Results suggested that at 800 nm femtosecond laser excitation, C1 and C2 showed strong two-photon induced upconversion fluorescence. The two-photon absorption cross-section of the compound was shown to be related to the substitution position of benzophenone. Molecular geometry optimization and electrochemistry suggested that the energies of the frontier orbitals and electron densities of C1 and C2 could be correlated to the position of benzophenone substitution as well.
[Show abstract][Hide abstract] ABSTRACT: Novel nitro-azobenzene dyes bearing one or two benzophenone branches were proposed and synthesized to improve their photophysical and photochemical properties. The new dyes exhibited double UV/visible bands, and they displayed weak fluorescence emission as excited at 350 nm. Single crystal X-ray diffraction data showed that two phenyl rings of azobenzene was almost coplanar, and the benzophenone part was neither coplanar nor linear connection with azobenzene via ether bridged bond, which have good fit with molecular geometry optimization calculation results. The cyclic voltammeric results of nitro-azobenzene dyes were firstly reported in this paper, which demonstrated that the electrochemical properties of nitro-azobenzene dyes was altered by the substitution of benzophenone part. Thermal stabilities of the new dyes were studied by the analysis of differential scanning calorimetry (DSC) and thermograving (TG) in this paper. Efficient visible-light photoinitiating polymerization of methyl methacrylate (MMA) by the novel nitro-azobenzene dyes was presented and discussed.
Journal of Fluorescence 12/2008; 19(3):533-44. · 1.79 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: In this paper, we have presented a range of new nitro-stilbene derivatives with benzophenones via ether or ester bridged bond. These nitro-stilbene derivatives with benzophenones have been conveniently obtained by condensation reaction. The linked benzophenones were efficiently introduced to nitro-stilbene dyes. The structures of these compounds have been characterized with NMR and element analysis. The single crystals of two target compounds (11 and 12) have been obtained, and their X-ray crystallographic data have been determined and discussed. Remarkably different absorption and fluorescence spectroscopy was observed for nitro-stilbene derivatives with benzophenones via different linked bonds. The results show that electron-donating or electron withdrawing bridged bonds have significant influence on the absorption and fluorescence spectroscopy, which makes it possible for the development of ideal nitro-stilbene dyes with benzophenones through chemical strategy.
Journal of Fluorescence 07/2008; 18(5):787-99. · 1.79 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: "A-B" type photosensitive compounds including two-photon chromophore and benzophenone moiety have been designed, synthesized and characterized. The UV-vis absorption and fluorescence emission of the compounds have been extensively studied in various solvents. The results show that the absorption of "A-B" type compounds displays obvious double absorption bands, one of which at short-wavelength is related to the benzophenone moiety, the other at long-wavelength is mainly contributed by chromophore. The emission of "A-B" type compounds at 500-700 nm shows an "unexpected" blue-shift comparing with that of the sole chromophore. The photosensitive compounds with amino group display strong emission in apolar solvents and have a low fluorescence quantum yields in polar solvents. In contrast, the compounds without amino group exhibit strong fluorescence emission in polar solvents, and low fluorescence quantum yields in apolar solvents. The fluorescence quantum yields of "A-B" type compounds are higher than those of the sole chromophore. The discoveries suggest that charge redistribution induced by the introduction of benzophenone moiety plays a key role on the absorption and emission spectroscopy.
Spectrochimica Acta Part A Molecular and Biomolecular Spectroscopy 11/2007; 70(5):1006-12. · 1.98 Impact Factor