Hongru Li

A Comprehensive Therotical Investigation of Intramolecular Proton Transfer in the Excited States for Some Newly-designed Diphenylethylene Derivatives Bearing 2-(2-Hydroxy-Phenyl)-Benzotriazole Part

This article presents a comprehensive therotical investigation of excited state intramolecular proton transfer (ESIPT) for some newly-designed diphenylethylene derivatives containing 2-(2-hydroxy-phenyl)-benzotriazole moiety with various substituted groups. The calculation shows the structural parameters and Mulliken charges of phototautomers enol (E) and keto (K) of these compounds exhibit no or tiny changes from S0 to S1. The calculated results suggest that HOMO and LUMO + 1 of the compounds displays excellent overlapping nature, and thus the absorption and emission could be from the electron transition of HOMO→LUMO + 1. The electron density distribution in the frontier orbital of E and K are influenced remarkably by various substituted groups in S0 and S1 states. Electron density distribution deficiency in 2-(2-hydroxy-phenyl)-benzotriazole part is observed in L + 1 for these derivatives. The calculation also suggests the potential energy curves of ESIPT are shown to be a strong relationship with electron donor-acceptor groups. The absorption spectra, normal emission spectra and ESIPT spectra of the derivatives were also calculated.

Synthesis, Crystal, Absorption and Fluorescence Spectroscopy of Nitro-Stilbene Derivatives with Benzophenones

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.

A Comprehensive Investigation on the Cooperative Branch Effect on the Optical Properties of Novel Conjugated Compounds

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.

Efficiently tuning the absorption and fluorescence spectroscopy of the novel branched p-nitro-stilbene derivatives with chemical strategy.

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-π-A” to “A-π-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.

A Successful Attempt to Obtain the Linear Dependence Between One-Photon and Two-Photon Spectral Properties and Hammett Parameters of Various Aromatic Substituents in New π-Extended Asymmetric Organic Chromophores

A series of new asymmetric chromophores containing aromatic substituents and possessing the excellent π-extension in space were prepared through multi-steps routes. One-photon and two-photon spectral properties of these new chromophores could be tuned by these substituents finely and simultaneously. The linear correlation of the wave numbers of the one-photon absorption and emission maxima to Hammett parameters of these substituents was presented. Near infrared two-photon absorption emission integrated areas of the target chromophores were correlated linearly to Hammett constants of these substituted groups.

Synthesis and Spectroscopy of Novel Branched Fluorescent Dyes Containing Benzophenone Parts and the Possibility as Fluorescence Probes

This paper describes a new fluorescent family of branched dyes containing benzophenone unit including 4-N, N-diphenylamino-4′-phenacyl-stilbene (C1), 4,4′-di(4-benzoylphenylethylene)yl-triphenylamine (C2) and 4,4′,4″-tri(4-benzoylphenylethylene)yl-triphenylamine (C3). Benzophenone part is coupled with core through C–C double bond. The chemical structures of the derivatives are characterized with 1H and 13C nuclear magnetic resonance and elemental analysis. Strong π–π stacking interactions are discovered with the analysis of the X-ray crystallographic data of C1. The absorption maxima and emission maxima of the derivatives exhibit gradual bathochromic shift from C1 to C3. The optical density of C1, C2 and C3 are shown to be related to the number of branches. The changes of dipole moments between the excited and ground states for C1, C2 and C3 were estimated to be 4.356, 8.091 and 8.479 Derby, respectively by Lippert equation, confirming that the internal charge transfer (ICT) dominates the process of excited singlet state. The possibility as fluorescence probes of the derivatives on the estimation of what region of micelles interacting with samples was evaluated.

Double Spectral theorem and Two Type Magnitude-Squared Coherence Functions

Studying frequency domain representation for the coherence between two signals is an important basic theoretical problem in the fundamental theories of signal processing. However, the old magnitude-squared coherence function (OMSCF) has been proved identical to 1, so that to cannot be used to extract any coherence information. Here, we will prove a core theorem in frequency domain coherence theories in signal processing, called as the double spectral theorem (DST). Based on the theorem, we presented the two types of new magnitude-squared coherence functions (MSCFs), called as the same type magnitude-squared coherence function (SMSCF) and the difference magnitude-squared coherence function (DMSCF) respectively, which were mathematically derived from DST and the conditions that they are equal to 1 or 0 can be theoretically derived from DST. Here, we further demonstrated that SMSCF and DMSCF could be used to exactly extract the coherence between two signals by each component

Double Spectral theorem and Two Type Magnitude Coherence Functions

Studying frequency domain representation for the coherence between two signals is an important basic theoretical problem in the fundamental theories of signal processing. However, magnitude-squared coherence function (MSCFs) could lose some phase information. Based on the core theorem in the frequency domain coherence theories, called as double spectral theorem (DST), we presented the two types of new magnitude coherence functions (MCFs), called as the same type magnitude coherence function (SMCF) and the difference magnitude coherence function (DMCF) respectively, which had been mathematically derived from DST and the conditions that they are equal to 1 or -1 or 0 were theoretically derived from DST. Here, we further demonstrated that SMCF and DMCF could be used to exactly extract the coherence between two signals by each component

The New Magnitude-Squared Coherence Functions and Their Properties Sensitive to Phase

Based on the core theorem of the frequency domain coherence in signal processing, called as double spectral theorem, we presented the two types of new magnitude-squared coherence function (MSCFs) in order to extract the coherence between two signals and gave the conditions that they are equal to 1 or 0. Here, we further studied their properties sensitive to initial phases of two signals and phase difference between two signals. Studying demonstrated that the two type MSCFs not only reflect frequency domain coherence of two signals, but also reflect phase relationship between two signals. One is sensitive to the phase difference between two signals and the other is either sensitive to the initial phases or phase difference between two signals. We call the properties as their properties sensitive to phaseBecause magnitude-squared coherence function (MSCFs) could lose some phase information, based on the core theorem for the frequency domain coherence in signal processing, called as double spectral theorem, we present the two types of new magnitude coherence functions (MCFs) in order to extract the coherence between two signals and give the conditions that they are equal to 0 or +1 or -1. Here, we further study their properties sensitive to initial phases of two signals and phase difference between two signals. Studying demonstrated that the two type MCFs not only reflect frequency domain coherence of two signals, but also reflect the phase relationship between two signals. One is sensitive to the phase difference between two signals and the other is either sensitive to the initial phases or the phase difference between two signals. We call the properties as their properties sensitive to phase