三乙胺与2-氯-5-甲氧基对苯醌光电子转移反应的CIDNP研究

用化学诱导动态核极化 (CIDNP)方法研究了三乙胺与 2 氯 5 甲氧基对苯醌在C6 D6 ,CD3CN溶剂中的反应机理 ,实验结果表明反应过程中首先形成基态电荷转移络合物 (CTC) ,在CD3CN中 ,光照电荷分离形成离子自由基对 ,使三乙胺亚甲基产生发射极化信号 .同时用UV

应用化学专业综合实验设计:光电子转移可行性判断

针对于光化学基本理论的实验教学对于应用化学专业的学生培养具有重要意义,将蒽与碘鎓盐的光电子转移可行性判断,以及蒽/碘鎓盐引发丙烯酸酯单体的聚合实验设计为应用化学专业的综合实验,以培养学生对光化学基本理论的理解。学生通过紫外-可见吸收光谱、荧光激发光谱和循环伏安实验获得实验数据,依据Rehm-Weller方程计算获得蒽与碘鎓盐之间光电子转移的自由能变,并通过光聚合实验学习光电子转移增感引发体系的应用。

Synthesis of Schiff Base Bearing Phenolic Hydroxy Group and Its Anion Recognition

A new anion receptor bearing phenolic hydroxy group based on 3,5- ditertbutylsalicylaldehyde-p-nitrophenylhydrazone （1） was designed and synthesized. Upon addition of AcO- and F-, the receptor exhibited visible color changes from deep yellow to purple. However, no obvious color changes were observed on addition of the other anions tested （H2PO4-, Cl-, Br-, I-）. The binding properties of the receptor with anions such as AcO and F- were investigated by UV-Vis and fluorescent titrations. The result indicated that the receptor 1 had a higher affinity to AcO- and F- and a 1：1 host-guest complex was formed through H-bond interactions between 1 and anions.

A Novel Sub-50nm Poly-Si Gate Patterning Technology

A novel low-cost sub-50nm poly-Si gate patterning technology is proposed and experimentally demonstrated.The technology is resolution-independent,ie.,it does not contain any critical photolithographic steps.The nano-scale masking pattern for gate formation is formed according to the image transfer of an edge-defined spacer.Experimental results reveal that the resultant gate length,about 75 to 85 percent of the thickness,is determined by the thickness of the film to form the spacer.From SEM photograph,the cross-section of the poly-Si gate is seen to be an inverted-trapezoid,which is useful to reduce the gate resistance.

Synthesis and photochemical properties of two ICT compounds with naphthalimide and diarylamine units

Two new diarylamine-substituted 1, 8-naphthalimide derivatives are synthesized by Cu I/18-crown-6/K2CO3 catalyst system and characterized by Fourier transform infrared （FT- IR）, ^1H-NMR and elemental analyses. The UV-vis absorption and photoluminescent （PL）spectra of the systems in n-hexane, tetrahydrofuran（THF）, and CH2Cl2 are investigated. These naphthalimide molecules have an absorption band centered at about 450 nm, which is assigned to an intramolecular chargetransfer （ICT）transition, and they emit light at 492, 501 nm in a nonpolar solvent such as n-hexane, and at 600, 620 nm in a polar solvent such as CH2Cl2. From the Lippert-Mataga equation, the difference of the dipole moment between the excited state and the ground state is estimated to be 9.2 and 9.8 D for 4- （ diphenylamine ）-N-（ 2-methoxyphenyl ）-1, 8-naphthalimide （ DMN-1 ） and 4-（ 2-naphthylphenylamine ）-N-（ 2- methoxyphenyl）-1, 8-naphthalimide （DMN-2）, respectively. This large change in the dipole moment upon excitation is typical for photoinduced ICT processes.

Photochemical Hydrogen Abstraction and Electron Transfer Reactions of Tetrachlorobenzoquinone with Pyrimidine Nucleobases

Pentachlorophenol, a widespread environmental pollutant that is possibly carcinogenic to humans, is metabolically oxidized to tetrachloroquinone （TCBQ） which can result in DNA damage. We have investigated the photochemical reaction dynamics of TCBQ with two pyrimidine type nucleobases （thymine and uracil） upon UVA （355 ran） excitation using the technique of nanosecond time-resolved laser flash photolysis. It has been found that 355 nm excitation populates TCBQ molecules to their triplet state 3TCBQ＊, which are highly reactive towards thymine or uracil and undergo two parallel reactions, the hydrogen abstraction and electron transfer, leading to the observed photoproducts of TCBQH. and TCBQ.- in transient absorption spectra. The concomitantly produced nucleobase radicals and radical cations are expected to induce a series of oxidative or strand cleavage damage to DNA afterwards. By characterizing the photochemical hydrogen abstraction and electron transfer reactions, our results provide potentially important molecular reaction mechanisms for understanding the carcinogenic effects of pentachlorophenol and its metabolites TCBQ.

Fluorescence Enhancement of Polyamine Derivatives of 1,8-Naphthalimide with Transition Metal Ions

A series of fluorescent chemosensors 1-3 were synthesized to detect transition metal ions. At the room temperature, fluorescence intensities of these chemosensors in acetonitrile without transition metal ions were found to be very weak, due to the process of the efficient intramolecular photoinduced electron transfer （PET）. However, after addition of the transition metal ions, the chemoscnsor 1-3 exhibits obvious fluorescence enhancement. Moreover, the intensity of the fluorescence emission of chemosensors increases significantly in the presence of Zn^2＋ and Cd^2＋. The fluorescent chemosensors with different polyamine as receptors show diverse affinity abilities to the transition metal ions and signal the receptor-metal ion interaction by the intensity change of fluorescence emission.

Review on heterophase/homophase junctions for efficient photocatalysis: The case of phase transition construction

Semiconductor photocatalysts are extensively applied in environmental treatment and energy conversion.However,one of their major disadvantages is their relatively low photocatalytic performance owing to the recombination of generated electron-hole pairs.The presence of the phase junction is an effective way to promote the photocatalytic activity by increasing the separation efficiency of the electron-hole pairs.Accordingly,extensive research has been conducted on the design of phase junctions of photocatalysts to improve their charge transfer properties and efficiencies.Therefore,for the design of an appropriate phase junction and the understanding of the mechanism of electron-hole separation,the development of the photocatalytic phase junction,including the preparation methods of the heterogeneous materials,is tremendously important and helpful.Herein,the commonly used,externally induced phase transformation fabrication techniques and the primary components of the semiconductors are reviewed.Future directions will still focus on the design and optimization of the phase junction of photocatalytic materials according to the phase transition with higher efficiencies for broadband responses and solar energy utilization.Additionally,the most popular phase transformation fabrication techniques of phase junctions are briefly reviewed from the application viewpoint.

Thermo‐driven photocatalytic CO reduction and H_(2) oxidation over ZnO via regulation of reactant gas adsorption electron transfer behavior

Photothermal catalysis is a widely researched field in which the reaction mechanism is usually investigated based on the photochemical behavior of the catalytic material.Considering that the adsorption of reactants is essential for catalytic reactions to occur,in this study,the synergistic effect of photothermal catalysis is innovatively elucidated in terms of the electron transfer behavior of reactant adsorption.For the H_(2)+O2 or CO+H_(2)reaction systems over a ZnO catalyst,UV irradiation at 25°C or heat without UV irradiation did not cause H_(2)oxidation or CO reduction;only photothermal conditions(100 or 150°C+UV light)initiated the two reactions.This result is related to the electron transfer behavior associated with the adsorption of CO or H_(2)on ZnO,in which H_(2)or CO that lost an electron could be oxidized by O2 or hydroxyls.However,the electron‐accepting CO could be reduced by the electron‐donating H_(2)into CH4 under photothermal conditions.Based on the in‐situ characterization and theoretical calculation results,it was established that the synergistic effect of the photothermal conditions acted on the(002)crystal surface of ZnO to stimulate the growth of zinc vacancies,which resulted in the formation of defect energy levels,adsorption sites,and an adjusted Fermi level.As a result,the electron transfer behavior between adsorbed CO or H_(2)and the crystal surface varied,which further affected the photocatalytic behavior.The results show that the effect of photothermal synergy may not only produce the expected kinetic energy,but more importantly,produce energy that can change the activation mode of the reactant gas.This study provides a new understanding of the CO catalytic oxidation and reduction processes over semiconductor materials.

Photophysical Properties of 4t-（p-aminophenyl）-2,2＇：6＇,2″-terpyridine

Spectral and photophysical investigations of 4＇-（p-aminophenyl）-2,2＇：6＇,2″-terpyridine （APT） have been performed in various solvents with different polarity and hydrogen-bonding ability. The emission spectra of APT are found to exhibit dual fluorescence in polar solvents, which attributes to the local excited and intramolecular charge transfer states, respectively. The two-state model is proven out for APT in polar solvent by the time-correlated single photon counting emission decay measurement. Interestingly, the linear relationships of different emission maxima and solvent polarity parameter are found for APT in protic and aprotic solvents, because of the hydrogen bond formation between APT and alcohols at the amino nitrogen N25. Furthermore, the effects of the complexation of the metal ion with tpy group of APT and the hydrogen bond formation between APT with methanol at the terpyridine nitrogen N4-NS-N14 are also presented. The appearance of new long-wave absorption and fluorescence bands indicates that a new ground state of the complexes is formed.

Electron transfer kinetics in CdS/Pt heterojunction photocatalyst during water splitting

Noble metal cocatalysts have shown great potential in boosting the performance of CdS in photocatalytic water splitting.However,the mechanism and kinetics of electron transfer in noble-metal-decorated CdS during practical hydrogen evolution is not clearly elucidated.Herein,Pt-nanoparticle-decorated CdS nanorods(CdS/Pt)are utilized as the model system to analyze the electron transfer kinetics in CdS/Pt heterojunction.Through femtosecond transient absorption spectroscopy,three dominating exciton quenching pathways are observed and assigned to the trapping of photogenerated electrons at shallow states,recombination of free electrons and trapped holes,and radiative recombination of locally photogenerated electron-hole pairs.The introduction of Pt cocatalyst can release the electrons trapped at the shallow states and construct an ultrafast electron transfer tunnel at the CdS/Pt interface.When CdS/Pt is dispersed in acetonitrile,the lifetime and rate for interfacial electron transfer are respectively calculated to be~5.5 ps and~3.5×10^(10) s^(−1).The CdS/Pt is again dispersed in water to simulate photocatalytic water splitting.The lifetime of the interfacial electron transfer decreases to~5.1 ps and the electron transfer rate increases to~4.9×10^(10) s^(−1),confirming that Pt nanoparticles serve as the main active sites of hydrogen evolution.This work reveals the role of Pt cocatalysts in enhancing the photocatalytic performance of CdS from the perspective of electron transfer kinetics.

Photophysical Property of Photoactive Molecules with Multibranched Push-Pull Structures

The structure-property characteristics of a series of newly synthesized intramolecular charge- transfer （ICT） compounds, single-branch monomer with triphenylmethane as electron donor and 2,1,3-benzothiadiazole as acceptor, the corresponding two-branch dimer and three- branch trimer, have been investigated by means of steady-state and femtosecond time- resolved stimulated emission fluorescence depletion （FS TR-SEP FD） techniques in different polar solvents. The TD-DFT calculations are further performed to explain the observed ICT properties. The interpretation of the experimental results is based on the comparative studies of the series of compounds which have increased amount of identical branch moiety. The similarity of the absorption and fluorescence spectra as well as strong solvent-dependence of the spectral properties for the three compounds reveal that the excited state of the dimer and trimer are nearly the same with that of the monomer, which may localize on one branch. It is found that polar excited state emerged through multidimensional intramolecular charge transfer from the donating moiety to the acceptor upon excitation, and quickly relaxed to one branch before emission. Even so, the red-shift in the absorption and emission spectra and decreased fluorescence radiative lifetime with respect to their monomer counterpart still suggest some extent delocalization of excited state in the dimer and trimer upon excitation. The similar behavior of their excited ICT state is demonstrated by FS TR-SEP FD measurements, and shows that the trimer has the largest charge-separate extent in all studied three samples. Finally, steady-state excitation anisotropy measurements has further been carried out to estimate the nature of the optical excitation and the mechanism of energy redistribution among the branches, where no plateau through the ICT band suggests the intramolecular excitation transfer process between the branches in dimer and trimer.

Synthesis of Porphyrin-Appended Pyridine as a Fluorescent Chemosensor for Cd（Ⅱ） and Hg（Ⅱ）

In this research, specific molecular sensors are classified according to the type of receptor-cation interaction, that is ligand-metal interactions. Receptors are based on a multidentate protoporphyrin-appended pyridine platform, which leaves at least a vacant coordination site for the incoming metal ions. A protoporphyrin-appended pyridine, 2,5-pyridine dicarboxyamidyl-8,13-bis（vinyl）-3,7,18,17-tetramethyl-21 H, 23 H-porphyrin（P-PTP）, was designed and synthesized. Its application as potential fluoroionophore for recognition of cadmium and mercury ions is reported. P-PTP shows chelation-enhanced fluorescence effect with Cd（Ⅱ） and Hg（Ⅱ） via the interruption of photoinduced electron transfer （PET） process, which has been utilized as the basis of the fabrication of the metal ions-sensitive fluorescent chemosensor. The analytical performance characteristics of the proposed Cd（Ⅱ）- and Hg（Ⅱ）- sensitive chemosensors were investigated. It shows a linear response toward Cd（Ⅱ） and Hg（Ⅱ） in the concentration range of 1.0×10-3 to 1.0×10-7 M with a limit of detection of 1.0×10-7 M and 0.5×10-7M for Cd（Ⅱ） and Hg（Ⅱ）, respectively. The chemosensor shows good selectivity for Cd（Ⅱ） over a large number of other transition metal ions, i.e., Cu（Ⅱ）, Zn（Ⅱ） and mixed metal ions.

Photoinduced Electron Transfer Between Mono-6-p-nitrobenzoyl-β- cyclodextrin and Adamantanamine-Cn-Co/Ni-porphyrins

Two series monot ailed porphyrins, Cobalt-5- {4- [ω- （1-adamant aneamino） alkyloxy] phenyl }- 10,15,20-triphenyl porphyrinate （CoPCnA, n=4,5,6） and Nickel-5-{4-[ω-（1-adamantaneamino）alkyloxy]phenyl}-10,15.20- triphenyl porphyrinate （NiPCnA, n=4,5,6）, were synthesized, in which the porphyrin moiety was connected to l-adamantanamine via a flexible hydrocarbon chain. The fluorescence quenching between these donor substrates and mono-6-p-nitrobenzoyl-β-cyclodextrin （NBCD） was studied in detail. Distinct fluorescence quenching occured in these supramolecular systems. This quenching was attributed to the photoinduced electron transfer （PET） inside the supramolecular assembly between the porphyrin donors and cyclodextrin acceptors. Detailed Stern-Volmer constants were measured and they were partitioned into dynamic Stern- Volmer quenching constants and static binding constants. It was demonstrated that the PET interaction between the porphyrin subunits and NBCD is indeed effective.

Photoinduced Electron Transfer in Dumbbell-type Fullerene Dyad

1,3-Dipolar cycloaddition of DTE-azomethine ylides （DTE： dithienyl-ethene） to C60 in refluxed toluene was used to synthesize novel dumbbell-type fullerene dimer 1. For the sake of comparison, the monoadduct 2 were also synthesized. The molecular geometries of these two compounds were determined by theoretical calculations with HF-3/21G method. UV-Vis and fluorescence experiments were carried out in solvents with different polarity at the room temperature. All the results indicated the existence of a photoinduced intramolecular electron transfer process between the donor and acceptor moieties.

Solvent Effects on Two-Photon Absorption of Alkyne and Alkene π-bridging Chromophores

The present work concerns the study of solvent effects on the geometrical structures, as well as one- and two-photon absorption （TPA） processes, for two series of alkyne and alkene π-bridging molecules, within the framework of the polarization continuum model. Particular emphasis was put on the characterization of solvent effects on the molecular geometrical structures and geometric distortion, which were measured by the bond-length-alternation parameter. The π centres in the compounds are seen to play a decisive role in increasing the TPA cross section and nonlinear optical properties. All studied molecules have relatively strong TPA characteristics, while the alkyne π-bridging ones yield larger TPA cross sections.

Energy Transfer and Electron Transfer in Composite System of Carbon Quantum Dots/Rhodamine B Molecules

In this work, we investigated the energy transfer (EnT) and electron transfer (ET) processes as well as their relationship in the carbon quantum dots/rhodamine B (CQDs/RhB) including o-CQDs/Rh B and m-CQDs/RhB systems by using photoluminescence spectroscopy in combination with steady-state and transient absorption spectroscopy. We found that the ET process is negligible in the o-CQDs/RhB system with an EnT efficiency as high as 73.2%,while it becomes pronounced in the m-CQDs/RhB system whose EnT efficiency is lower than 33.5%. Such an interplay of En T and ET processes revealed in the prototypical composite system consisting of carbon quantum dots and dye molecules would provide helpful insights for applications of relevance to exciton quenching.

Optical Properties and Response Mechanism Analysis of Multi-branched Fluorescent Probes Based on Intramolecular Charge Transfer

In this work, the optical properties of fluorescent probes used for detection of biothiol were studied by employing time-dependent density functional theory. By calculating the single photon absorption and emission properties of probe Mol.1, Mol.2 and Mol.3 before and after reaction with cysteine and homocysteine, we have investigated the effect of carboncarbon triple bond and benzene ring on the properties of fluorescent probes. It is found that the oscillator strength of probe molecules increases gradually with the improvement of the structure of the electron donor triphenylamine and the addition of carbon-carbon triple bonds, and better properties of fluorescence probes have also been demonstrated. At the same time, the effect of different number of side branches on the molecular properties of the probe was also studied. The results showed that compared with single-branched molecule Z1 and tribranched probe Mol.3, two side probe molecules Z2 had higher oscillator strength and better detection effect. In addition, the new single-branched probe Mol.4 with the addition of carbon-carbon triple bonds and benzene rings has better probe properties and simpler structure than the tribranched probe Mol.3.

Relative Molecular Orientations in Organic Optoelectronic Films Probed via Polarization-Selected UV/IR Mixed Frequency Ultrafast Spectroscopy

Molecular packing patterns are crucial factors determining electron/energy transfer processes that are critical for the optoelectronic properties of organic thin film devices.Herein,the polarization-selective ultraviolet/infrared(UV/IR)mixed frequency ultrafast spectroscopy is applied to investigate the relative molecular orientations in two organic thin films of 7-(diethylamino)coumarin-3-carboxylic acid(DEAC)and perylene.The signal anisotropy changes caused by intermolecular energy/electron transfers are utilized to calculate the cross angles between the electronic transition dipole moment of the donor and the vibrational transition dipole moments of the acceptor,yielding the relative orientation between two adjacent molecules.Using this method,the relative orientation angle in DEAC film is determined to be 53.4°,close to 60°of its single crystalline structure,and that of the perylene film is determined to be 6.2°,also close to-0.2°of its single crystalline structure.Besides experimental uncertainties,the small difference between the angles determined by this method and those of single crystals also results from the fact that the thin film samples are polycrystalline where some of the molecules are amorphous.

Transition Dipole, Charge Transfer, and Electron-hole Coherence in Two-photon Absorption： Visualizations with Two Dimensional Site and Three Dimensional Cube Representations

The developed visualization methods of two dimensional （2D） site and three dimensional （3D） cube representations have been performed to show the orientation of transition dipole, charge transfer, and electron-hole coherence in two-photon absorption （TPA）. The 3D cube representations of transition density can reveal visually the orientation and strength of transition dipole moment, and charge different density show the orientation of charge transfer in TPA. The 2D site representation can reveal visually the electron-hole coherence in TPA. The combination of 2D site and 3D cube representations provide clearly inspect into the charge transfer process and the contribution of excited molecular segments for TPA.