Substituent effect of fluorine atom on benzothiadiazole bridging unit in dye sensitized solar cells

Dye sensitized solar cells performances using two organic dyes with fluorinated-benzothiadiazole spacer, 3-{5-[7-(5-{4-[Bis(9,9-dimethyl-9H-fluoren-2-yl)-amino]-5-fluoro-phenyl}thiophen-2-yl)benzo-[1,2,5]thiadiazol-4-yl]thiophen-2-yl}-2-cyano acrylic acid (JK-311) and 3-{5-[7-(5-{4-[Bis(9,9-dimethyl-9H-fluoren-2-yl)-amino]-5,6-difluorophe-nyl}thiophen-2-yl)benzo-[1,2,5]thiadiazol-4-yl]thiophen-2-yl}-2-cyano acrylic acid (JK-312), were systematically investigated by solar simulation equipment, stepped light-induced transient measurements of photocurrent and voltage, and electrochemical impedance spectroscopy. To investigate substituent effect of fluorine atom on benzothiadiazole, molecular orbital calculations of two dyes using a time dependent density functional theory model with B3LYP/3-31G* were also carried out. JK-312 showed a unique electronic transition from HOMO-1 to LUMO. Short circuit current and open-circuit voltage in DSSCs performances were increased by the introduction of fluorine atom into spacer segment, compared to fluorine-free dyes.     

2,4和8-支噁二唑衍生物的三光子吸收和三光子上转换荧光

用飞秒Ti:sapphire激光测定了3个对称噁二唑衍生物4-{N,N-双[4-(4-[5-(4-叔丁基苯基)-1,3,4-噁二唑-2]苯乙烯基)苯基]氨基}苯甲醛(Bis-oxa)、2,5-双{4-[2-N,N-双(4-{4-[5-(4-叔丁基苯基)-1,3,4-噁二唑-2]苯乙烯基}苯基)氨基苯乙烯基]苯基}-1,3,4-噁二唑(Quadri-oxa)和2,5-双(4-{2-N,N-双[({3,5-二[5-(4-叔丁基苯基)-1,3,4-噁二唑-2]苯基}乙烯基)苯基]氨基苯乙烯基}苯基)-1,3,4-噁二唑(Octu-oxa)的三光子吸收谱和三光子荧光光谱. 在1260 nm飞秒激光激发下, 2,4和8-支噁二唑衍生物的三光子吸收系数分别为5.0×10^-5, 10.0×10^-5和10.0×10^-5 cm³/GW², 三光子频率上转换荧光发射波长分别为533, 544和551 nm. 研究了多支化合物线性吸收和透过、单光子荧光及量子产率、荧光寿命、多光子荧光光谱和三光子吸收系数谱. 对称多支噁二唑衍生物具有很强的三光子吸收和上转换荧光性质.     

Molecular engineering of organic sensitizers for dye-sensitized solar cell applications

Novel unsymmetrical organic sensitizers comprising donor, electron-conducting, and anchoring groups were engineered at a molecular level and synthesized for sensitization of mesoscopic titanium dioxide injection solar cells. The unsymmetrical organic sensitizers 3-(5-(4-(diphenylamino)styryl)thiophen-2-yl)-2-cyanoacrylic acid (D5), 3-(5-bis(4-(diphenylamino)styryl)thiophen-2-yl)-2-cyanoacrylic acid (D7), 5-(4-(bis(4-methoxyphenylamino)styryl)thiophen-2-yl)-2-cyanoacrylic acid (D9), and 3-(5-bis(4,4'-dimethoxydiphenylamino)styryl)thiophen-2-yl)-2-cyanoacrylic acid (D11) anchored onto TiO2 and were tested in dye-sensitized solar cell with a volatile electrolyte. The monochromatic incident photon-to-current conversion efficiency of these sensitizers is above 80%, and D11-sensitized solar cells yield a short-circuit photocurrent density of 13.90 +/- 0.2 mA/cm(2), an open-circuit voltage of 740 +/- 10 mV, and a fill factor of 0.70 +/- 0.02, corresponding to an overall conversion efficiency of 7.20% under standard AM 1.5 sun light. Detailed investigations of these sensitizers reveal that the long electron lifetime is responsible for differences in observed open-circuit potential of the cell. As an alternative to liquid electrolyte cells, a solid-state organic hole transporter is used in combination with the D9 sensitizer, which exhibited an efficiency of 3.25%. Density functional theory/time-dependent density functional theory calculations have been employed to gain insight into the electronic structure and excited states of the investigated species.     

以N为耦合中心多枝分子的双光子上转换荧光

采用非线性透过率法研究了以N为耦合中心的多枝化合物N-[4-{2-(3,5-二-[5-(4-叔丁基苯基)-1,3,4-噁二唑-2-]苯基}-1-乙烯基}苯基}-N,N-二苯胺(BPODPA), N,N-双[4-{2-(3,5-二-[5-(4-叔丁基苯基)-1,3,4-噁二唑-2-]苯基}-1-乙烯基}苯基}-N-苯胺(BBPOPA)和N,N,N-三[4-{2-(3,5-二-[5-(4-叔丁基苯基)-1,3,4-噁二唑-2]苯基}-1-乙烯基}苯基}胺(TBPOA)的双光子吸收性质, 测定了化合物的单光子荧光光谱和双光子上转换荧光光谱, 研究了多枝化对三苯胺分子双光子吸收和双光子激发荧光性质的影响.在800 nm波长的激光激发下,化合物BPODPA、BBPOPA和TBPOA在二氯甲烷溶液中发出很强的蓝绿色双光子上转换荧光, 荧光峰分别位于502、515 和518 nm. 这些多枝结构化合物的双光子吸收截面较大, 双光子吸收增强来源于多枝分子中扩展的π共轭体系和重复单元的协同效应.     

对称4-枝和8-枝噁二唑衍生物的合成与荧光性质

采用Wittig-Horner和Heck反应合成了3个对称多枝[1,3,4]-噁二唑衍生物2,5-双{4-{4-[N,N-二(4-溴苯基)-氨基] 苯乙烯基}苯基}-1,3,4-噁二唑(BrPASPO), 2,5-双{4-{4-{N,N-二{4-{4-[5-(4-叔丁基苯基)-1,3,4-噁二唑基-2-]苯乙烯基}苯基}氨基}苯乙烯基}苯基}-1,3,4-噁二唑(TPASPO)和2,5-双{4-{4-{N,N-二{4-{3,5-二[5-(4-叔丁基苯基)-1,3,4-噁二唑基-2]-苯乙烯基}苯基}氨基}苯乙烯基}苯基}-1,3,4-噁二唑(OPASPO). 目标化合物的结构经过红外光谱、核磁共振氢谱、质谱和熔点确认. 在CH2Cl2溶液中三者的最大吸收波长分别在403 (BrPASPO), 408 (TPASPO)和409 nm (OPASPO), 荧光发射峰分别为495 (BrPASPO), 509 (TPASPO)和506 nm (OPASPO). 化合物TPASPO和OPASPO在CH2Cl2溶液中的荧光量子产率分别为0.47和0.45. 8枝化合物的荧光寿命高于4枝化合物. 对称多枝化合物具有很强的分子内电荷转移能力和荧光发射能力.     

敏化染料分子长径比对太阳能电池性能的影响

采用同一系列但分子长径比不同的3种染料:2-氰基-3-[2-[4-{2-[4-N,N-二(4-甲基苯基)氨基苯基]乙烯基}-苯基氨基)-嘧啶-5-取代基]-丙烯酸(MTPA-Pyc)、2-氰基-3-(4-{2-[4-N,N-二(4-甲基苯基)氨基苯基]乙烯基}-苯基)-丙烯酸(MTPAcc)和2-氰基-3-[4-N,N-二(4-甲基苯基)氨基苯基]-丙烯酸(MTPAc),研究了在不同吸附溶剂中3种染料分子在Ti O2上的吸附量和聚集态,探讨了敏化染料分子长径比对染料敏化太阳电池性能的影响.结果表明,MTPAcc具有最合适的分子长径比,其在Ti O2表面的吸附量及应用的光电性能最高;吸附溶剂的极性增大有利于提高染料的吸附量,但也会影响染料分子的聚集态.当以四氢呋喃为吸附溶剂时,MTPAcc在Ti O2表面的吸附量大且不发生聚集,对应的敏化太阳能电池器件在所有结果中表现最好,在490 nm处的单色光光电转化效率(IPCE)极值达到84%,总光电转化效率(η)达到5.72%.     

双枝[1,3,4]-噁二唑衍生物的合成与荧光性质

通过Wittig反应和Heck反应合成了三个双枝噁二唑衍生物: N-{{{3,5-二-[5-(4-叔丁基苯基)-1,3,4-噁二唑-2]-苯基}-E-乙烯基}-4-苯基}二苯胺(BBOD-2), N,N-双{{{3,5-二-[5-(4-叔丁基苯基)-1,3,4-噁二唑-2]-苯基}-E-乙烯基}-4-苯基}苯胺(BBOD-3), N,N,N-三{4-{2-{3,5-二-[5-(4-叔丁基苯基)-1,3,4-噁二唑-2]-苯基}-E-乙烯基}苯基}胺(BBOD-4). 化合物结构经过红外光谱、核磁共振谱、质谱和熔点确证, 测定了它们在不同溶剂中的紫外光谱和单光子荧光光谱. BBOD-1, BBOD-2, BBOD-3, BBOD-4在二氯甲烷中的最大吸收峰分别位于295, 390, 398和408 nm; 最大发射峰分别为360, 486, 483和487 nm. 讨论了Stokes位移与溶剂极性的关系.     

Design Approach of Lifetime Extending Thermally Activated Delayed Fluorescence Sensitizers for Highly Efficient Fluorescence Devices

In this work, a design approach of three thermally activated delayed fluorescence (TADF) emitters to extend the device lifetime of the TADF sensitized fluorescent devices was studied. Three TADF materials, 5-{4,6-bis[4-(tert-butyl)phenyl]-1,3,5-triazin-2-yl}-2-(10,15-diphenyl-10,15-dihydro-5H-diindolo[3,2-a:3′,2′-c]carbazol-5-yl)benzonitrile (tTCNTruX), 4-[3-cyano-4-(10,15-diphenyl-10,15-dihydro-5H-diindolo[3,2-a:3′,2′-c]carbazol-5-yl)phenyl]-2,6-diphenylpyrimidine-5-carbonitrile (PCNTruX) and 4-(4-{10,15-bis[4-(tert-butyl)phenyl]-10,15-dihydro-5H-diindolo[3,2-a:3′,2′-c]carbazol-5-yl}-3-cyanophenyl)-2,6-diphenylpyrimidine-5-carbonitrile (PCNtTruX), were synthesized as sensitizers for TADF-sensitized fluorescent organic light-emitting diodes. The two tTCNTruX and PCNtTruX TADF emitters were designed to have Dexter energy transfer with blocking groups either in the donor or acceptor unit of the donor–acceptor-type TADF sensitizer. The TADF materials showed small singlet–triplet energy splitting and a high reverse intersystem crossing (RISC) rate for effective sensitization of the fluorescent emission of the fluorescent emitter. tTCNTruX- and PCNtTruX-sensitized fluorescent devices showed maximum external quantum efficiencies (EQEs) of 17.7 % and 11.5 % in the yellow and red devices, respectively, which were higher than those of TADF-sensitized devices with the corresponding TADF sensitizer without a blocking group. Moreover, the device lifetime was also extended by employing the tTCNTruX and PCNtTruX sensitizers. This work demonstrated that the tTCNTruX and PCNtTruX sensitizers are effective to improve the maximum EQE and device lifetime of TADF-sensitized fluorescent devices.     

2,7-Diaminofluorene-based organic dyes for dye-sensitized solar cells: effect of auxiliary donor on optical and electrochemical properties

New organic dyes containing a diarylaminofluorene unit as an electron donor and cyanoacrylic acid as acceptor and anchoring group in a donor-π-donor-π-acceptor architecture have been synthesized and characterized as sensitizers for nanocrystalline TiO(2)-based dye-sensitized solar cells. They have shown three major electronic absorptions originating from the π-π* and charge-transfer transitions covering the broad visible range (250-550 nm) in solution. The charge-transfer transition of the dyes exhibited negative solvatochromism, suggesting a polarized ground state. They have also displayed acidochromism in solution owing to the presence of a protonation-deprotonation equilibrium. On comparison with the triphenylamine and carbazole-based parent dyes (E)-2-cyano-3-(4-(diphenylamino)phenyl)acrylic acid and (E)-2-cyano-3-(9-ethyl-9H-carbazol-3-yl)acrylic acid they exhibited longer wavelength absorptions and facile oxidation, indicating the stronger electron-donating ability of the auxiliary chromophores. In addition, they exhibited nearly two times larger light-to-electron conversion efficiency under simulated AM 1.5 G irradiation (100 mW cm(-2)) with an aperture mask when compared to the parent dyes. Among the new dyes, the one containing the naphthylphenylamine segment showed better device characteristics attributable to the higher HOMO energy level which probably facilitates the regeneration of the dye and effective suppression of the back reaction of the injected electrons with the I(3)(-) in the electrolyte. The optical properties of the dyes were modeled using TDDFT simulations employing different theoretical models (B3LYP, CAM-B3LYP, and MPW1K), and the best correlations with the observed parameters have been found for CAM-B3LYP and MPW1K calculations. The electron lifetimes extracted from the electrochemical impedance measurements of the dye-sensitized solar cells were used to interpret the solar cell efficiency alternations.     

Glycosylated star-shaped conjugated oligomers for targeted two-photon fluorescence imaging

A glucopyranose functionalized star-shaped oligomer, N-tris{4,4',4'-[(1E)-2-(2-{(E)-2-[4-(benzo[d]thiazol-2-yl)phenyl]vinyl}-9,9-bis(6-2-amido-2-deoxy-1-thio-β-D-glucopyranose-hexyl)-9H-fluoren-7-yl)vinyl]phenyl}phenylamine (TVFVBN-S-NH(2)), is synthesized for two-photon fluorescence imaging. In water, TVFVBN-S-NH(2) self-assembles into nanoparticles with an average diameter of ～49?nm and shows a fluorescence quantum yield of 0.21. Two-photon fluorescence measurements reveal that TVFVBN-S-NH(2) has a two-photon absorption cross-section of ～1100 GM at 780?nm in water. The active amine group on the glucopyranose moiety allows further functionalization of TVFVBN-S-NH(2) with folic acid to yield TVFVBN-S-NH(2) FA with similar optical and physical properties as those for TVFVBN-S-NH(2). Cellular imaging studies reveal that TVFVBN-S-NH(2) FA has increased uptake by MCF-7 cells relative to that for TVFVBN-S-NH(2), due to specific interactions between folic acid and folate receptors on the MCF-7 cell membrane. This study demonstrates the effectiveness of glycosylation as a molecular engineering strategy to yield water-soluble materials with a large two-photon absorption (TPA) cross-section for targeted cancer-cell imaging.     

Molecular engineering of organic sensitizers containing p-phenylene vinylene unit for dye-sensitized solar cells

Three organic sensitizers containing bis-dimethylfluorenyl amino donor and a cyanoacrylic acid acceptor bridged by p-phenylene vinylene unit were synthesized. The power conversion efficiency was quite sensitive to the length of bridged phenylene vinylene groups. A nanocrystalline TiO2 dye-sensitized solar cell was fabricated using three sensitizers. The maximum power conversion efficiency of JK-59 reached 7.02%.     

N-（取代苯基哌嗪基烷基）酰胺类α_1-受体拮抗剂的设计、合成及生物活性研究

结合苯基哌基类α_1-受体拮抗剂的构效关系和我们应用计算机辅助药物设计 方法所构建的药效团模型,设计并合成了呋喃-2-甲酸{ω-[4-（取代苯基）-1-哌 嗪基]-烷基}酰胺和2-氧代-2H-苯并吡喃-3-羧酸{ω-[4-（取代苯基）-1-哌嗪基]- 烷基}酰胺两类衍生物,其结构经~1H NMR,IR及MS（HRMS）确证。初步生物活性测 试表明,所合成的目标化合物多数具有较好的α_1-受体拮抗剂,良性前列腺增生 。     

Synthesis and Biological Activity of 5-Aryl-N-{4-[(1,3-thiazol-2-yl)sulfamoyl]phenyl}-1-phenyl-1H-pyrazole-3-carboxamides and Their Salts

Russian Journal of General Chemistry - The reaction of 4-aryl-2-hydroxy-4-oxo-N-{4-[(1,3-thiazol-2-yl)sulfamoyl]phenyl}but-2-enamides with phenylhydrazine in glacial acetic acid afforded...     

Design,Synthesis, and Anticancer Evaluation of 2-{3-{4-[(5-Aryl-1,2,4-oxadiazol-3-yl)methoxy]phenyl}isoxazol-5-yl}-N-(3,4,5-trimethylphenyl)thiazol-4-amine Derivatives

Russian Journal of General Chemistry - A series of new 2-{3-{4-[(5-aryl-1,2,4-oxadiazol-3-yl)methoxy]phenyl}isoxazol-5-yl}-N-(3,4,5-tri-methylphenyl)thiazol-4-amine derivatives is synthesized, and...     

Design,Synthesis, and Anticancer Evaluation of N-(4-{5-[4-(5-Methyl-1,3,4-oxadiazol-2-yl)phenyl]-4-(2,3,4-trimethoxyphenyl)-1,3-thiazol-2-yl}phenyl)benzamides

Russian Journal of Organic Chemistry - A series of substituted N-(4-{5-[4-(5-methyl-1,3,4-oxadiazol-2-yl)phenyl]-4-(2,3,4-trimethoxy­phenyl)-1,3-thiazol-2-yl}phenyl)benzamides were designed...     

Synthesis and some transformations of methyl [4-(oxoacetyl)phenyl]carbamate

The oxidation of methyl (4-acetylphenyl)carbamate with selenium dioxide in dioxane–water (30: 1) gave methyl [4-(oxoacetyl)phenyl]carbamate whose condensation with ethyl acetoacetate or diethyl malonate and hydrazine hydrate afforded ethyl 3-methyl-6-[4-(methoxycarbonylamino)phenyl]pyridazine-4-carboxylate and methyl {4-[5-(hydrazinecarbonyl)-6-oxo-1,6-dihydropyridazin-3-yl]phenyl}carbamate, respectively. The reaction of methyl [4-(oxoacetyl)phenyl]carbamate with o-phenylenediamine in dimethylformamide–ethanol on heating led to the formation of methyl [4-(quinoxalin-2-yl)phenyl]carbamate. Methyl {4-(5,7-dioxo- 4,4a,5,6,7,8-hexahydropyrimido[4,5-c]pyridazin-3-yl)phenyl}carbamate and methyl {4-(5-oxo-7-sulfanylidene- 4,4a,5,6,7,8-hexahydropyrimido[4,5-c]pyridazin-3-yl)phenyl}carbamate were synthesized by reactions of methyl [4-(oxoacetyl)phenyl]carbamate with barbituric and thiobarbituric acids, respectively, and hydrazine hydrate in the presence of zirconyl chloride octahydrate at room temperature.     

New type of organic sensitizers with a planar amine unit for efficient dye-sensitized solar cells

A new type of organic sensitizers incorporating a planar amine unit have been synthesized and demonstrated to be a highly efficient sensitizers, showing evidence of lateral interactions on the TiO(2) surface. Under standard global air mass 1.5 solar conditions, the JK-98 sensitized cell gave a short circuit photocurrent density (J(sc)) of 16.78 mA cm(-2), an open-circuit voltage (V(oc)) of 0.745 V, and a fill factor (ff) of 0.70, corresponding to an overall conversion efficiency (η) of 8.71%.     

Reaction of 2-aminothiophenol with acrylic acid and conversion of the resultant adducts

The reaction of acrylic acid with 2-aminothiophenol gives 5-carboxyethyl-2,3-dihydro-5H-benzo[b][1,4]-thiazepin-4-one and N-[2-(carboxyethylthio)phenyl]-α-alanine, while the reaction of acrylic acid with bis(2-aminophenyl) disulfide gives bis[2-(carboxyethylamino)phenyl] disulfide. The action of potassium thiocyanate in acid medium on the carboxyethylamino derivatives yields 1-[2-carboxyethylthio)phenyl]dihydro-4(1H,3H)-pyrimidinone-2-thione, bis-{2-[dihydro-4(1H, 3H)-pyrimidinone-2-thion-1-yl]phenyl} disulfide, and 3-(2-mercaptobenzothiazol-3-yl)propanoic acid. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 256–261, February, 2006.     

吡啶星型分子的双光子上转换荧光特性

用飞秒Ti:sapphire激光测定了一种星型吡啶分子2,5-二{4-{4-[N,N-二(4-吡啶乙烯基)苯基氨基]苯乙烯基}苯基}-1,3,4-噁二唑(PyPASPO)的双光子吸收截面及上转换荧光光谱.采用非线性透过率法测得二氯甲烷和四氢呋喃溶液中的其双光子吸收截面分别为412.5 和288.8 GM. 系统研究了吡啶星形分子PyPASPO的线性吸收和透过、单光子荧光、荧光寿命及激发-发射三维荧光谱和前线轨道能级. 在800 nm和150 fs钛宝石激光器激发下PyPASPO在二氯甲烷和四氢呋喃溶液中的双光子上转换荧光发射波长分别位于571和 525 nm,在二氯甲烷溶液中单光子荧光峰位于532 nm,荧光寿命为1.24 ns. HOMO和LUMO能级分别为-5.21 eV和-2.92 eV.增大分子内电荷转移有效增强了吡啶星形分子的双光子吸收和双光子上转换荧光发射能力     

Synthesis and oxidation of triarylamine derivatives bearing hydrogen-bonding groups

Hydrogen-bonding triarylamines, 4-(N,N-bis(4-methoxyphenyl)amino)benzoic acid (TPA1), 5-(N,N-bis(4-methoxyphenyl)amino)isophthalic acid (TPA2), and N-(4-(1H-benzimidazol-2-yl)phenyl)-N,N-bis(4-methoxyphenyl)amine (BImTPA), were synthesized as radical cation precursors. TPA1 and TPA2 are readily p-doped by AgSbF(6) to give highly persistent radical cations. Poor solid-state spin yields of the radical cation from BImTPA may be due to spin delocalization.