吲哚染料的电荷转移和能量转移:应用于无金属的染料敏感太阳能电池

Metal-free indoline dyes for dye-sensitized solar cells were studied by employing quantum chemistry methods.Comparative study of the properties of both ground and excited states of metal-free indoline dyes for dye-sensitized solar cells revealed: (i) as the number of rhodanine rings increases, the energy di?erence betweenHOMO and LUMO decreases and there is a red shift in the absorption spectrum with the binding energyincreased, and the transition dipole moment decreased; (ii) Based on an analysis of charge di?erential density,we observed that the charge and energy are transfered from the phenylethenyl to the indoline and rhodaninerings; (iii) The electron-hole coherences are mainly on the indoline and rhodanine rings, and the exciton sizesare 30 and 40 atoms for indoline dyes with one and two rhodanline rings, respectively. These results serveas a good example of computer-aided design in metal-free indoline dyes for dye-sensitized solar cells.     

Highly efficient new indoline dye having strong electron-withdrawing group for zinc oxide dye-sensitized solar cell

New indoline dye (DN319) having strong electron-withdrawing dicyanovinylidene moiety and octyl group in the terminal rhodanine ring gave higher efficiency than D205, which was known as an excellent organic dye sensitizer. This result is attributed to the bathochromic shift in the UV-vis absorption band and positive shift in the E_ox level of DN319.     

N-(2-Alkoxyphenyl)-substituted double rhodanine indoline dyes for zinc oxide dye-sensitized solar cell

The effect of N-(2-alkoxyphenyl) group in double rhodanine indoline dye on the performance of zinc oxide dye-sensitized solar cell was examined. Both J_sc and V_oc were improved by introducing long alkoxy group due to prevention of H-aggregates formation and inhibition of electron recombination from zinc oxide surface to electrolyte.     

Triple domino reaction for the synthesis of pyrazole/indoline linked chromenes

A simple and convenient method towards the synthesis of highly diversified chromenopyrazole/indoline frameworks in excellent yields via iodine promoted triple domino reaction involving Michael addition followed by intramolecular cyclization and dehydrogenation sequence has been described for the first time.     

二氢吲哚类染料用于染料敏化太阳能电池光敏剂的比较

采用密度泛函理论(DFT)和含时密度泛函理论(TD-DFT)对四种二氢吲哚染料进行研究, 从中筛选出相对优秀的染料敏化太阳能电池光敏剂. 对前线分子轨道的计算表明, 二氢吲哚染料的前线分子轨道结构非常有利于染料激发态向TiO2电极的电子注入. 对真空中的紫外和可见光吸收光谱的计算表明, 二氢吲哚染料的吸收光谱与太阳辐射光谱匹配较好. 对染料分子的能级计算表明, 二氢吲哚染料的能级结构比较适合于I-/I-3作电解液的TiO2纳米晶太阳能电池的光敏剂. 二氢吲哚染料最低未占据分子轨道(LUMO) 能级均比TiO2晶体导带边能级高, 能够保证激发态染料分子高效地向TiO2电极转移电子. 二氢吲哚染料最高占据分子轨道(HOMO)的能级比I-/I-3能级低, 保证了失去电子的染料分子能够顺利地从电解液中得到电子. 与实验数据比较, 得出在提高染料敏化太阳能电池转换效率方面, 对染料的关键要求是LUMO能级的位置. 染料分子的稳定性是染料敏化太阳能电池使用寿命的关键因素. 通过对化学键键长的比较表明, 二氢吲哚染料的分子稳定性基本相同. 对计算结果的分析表明, 二氢吲哚染料1(ID1)的LUMO能级最高, 分子稳定性最好, 在酒精溶液中的吸收光谱与太阳辐射光谱匹配很好, 在同类染料中是较好的染料敏化太阳能电池光敏剂.     

Synthesis of (−)-Dihydroraputindole D by Enantioselective Benzoylation of a 1,3-Diol Intermediate

The enantioselective synthesis of (−)-dihydroraputindole D is reported. The key step is the desymmetrizing benzoylation of a prochiral 1,3-diol employing Trost′s ProPhenol catalyst system, which has been applied for the first time to a cyclic molecule carrying geminal hydroxymethyl groups. The cyclopenta[f]indoline system was assembled by Au(I)-catalyzed cyclization of an alkynylated indoline precursor. (−)-Dihydroraputindole D was obtained in 17 steps and 8% overall yield starting from dihydroxyacetone. In combination with quantum chemical calculations of the ECD spectra, our synthesis allowed us to determine the absolute configuration (5S,7R) of the natural product (+)-raputindole D from the Rutaceous plant Raputia simulans.     

High-conversion-efficiency organic dye-sensitized solar cells with a novel indoline dye

An indoline dye (D205), the synthesis method of which is disclosed in this report, gave high-efficiency organic dye-sensitized solar cells (9.52%) using an anti-aggregation reagent (chenodeoxycholic acid).     

Condensation of rhodanine withβ-dicarbonyl compounds

Reaction of acetylacetone with rhodanine in ethanol solution, in the presence of ammonia and ammonium chloride gives two condensation products, containing one or two rhodanine groups. Under the same conditions benzoylacetone condenses with one molecule of rhodanine. Methylation of these compounds with methyl iodide takes place at an exocyclic sulfur atom, to give mono- and dimethylmercapto derivatives. The condensation products from the above carbonyl compounds and rhodanine have an active methylene group which can react with nitroso compounds and diazonium salts.     

Preferential Face‐on and Edge‐on Orientation of Thiophene Oligomers by Rational Molecular Design

Precise control over the supramolecular organization of organic semiconducting materials guiding to exclusive face‐on or edge‐on orientation is a challenging task. In the present work, we study the preferential packing of thiophene oligomers induced through rational molecular designing and self‐assembly. The acceptor–donor–acceptor‐type oligomers having 2‐(1,1‐dicyano‐methylene)rhodanine as acceptor ( OT1 ) favored a face‐on packing, whereas that of functionalized with N‐octyl rhodanine ( OT2 ) preferred an edge‐on packing as evident from 2D‐grazing incidence angle X‐ray diffraction, tapping‐mode atomic force microscopy (AFM) and Raman spectroscopy analyses. The oligomers exhibited anisotropic conductivity in the self‐assembled state as an outcome of the preferred orientation, revealed by the conducting AFM experiment.     

6'-对位取代苯乙烯基吲哚啉螺吡喃的合成

利用2-亚甲基吲哚啉和取代水杨醛缩合得到十三种新的烷基苯乙烯基吲哚啉螺苯并吡喃。在苯并吡喃部分含有硝基的螺吡喃显示出逆光致变色行为，其它的则为普通光致变色化合物。同时，结果表明，化合物异构体的稳定性不仅取决于化合物本身的结构，而且还取决于介质环境的影响。     

6′-对位取代苯乙烯基吲哚啉螺吡喃的合成

利用2-亚甲基吲哚啉和取代水杨醛缩合得到十三种新的烷基苯乙烯基吲哚啉螺苯并吡喃。在苯并吡喃部分含有硝基的螺吡喃显示出逆光致变色行为,其它的则为普通光致变色化合物。同时,结果表明,化合物异构体的稳定性不仅取决于化合物本身的结构,而且还取决于介质环境的影响。     

A new strychnobrasiline base of Strychnos mattogrossensis

A new strychnobrasiline derivative, 12-hydroxy-10,11-dimethoxystrychnobrasiline 1, has been isolated from the stem barks of Strychnos mattogrossensis. Its structure was established by spectroscopy analysis (1D and 2D NMR, MS, IR, UV) and literature data comparison. Two other known indoline alkaloids were also obtained from the heartwood, 12-hydroxy-11-methoxystrychnobrasiline 2 and strychnobrasiline 3.     

A novel class of inhibitors for human and rat steroid 5alpha-reductases: synthesis and biological evaluation of indoline and aniline derivatives. III

While searching for novel nonsteroidal inhibitors of human and rat prostatic 5alpha-reductases, we found a new series of indoline and aniline derivatives that showed potent inhibitory activities for both enzymes. Among them, 3-chloro-4-?[1-(4-phenoxybenzyl)indolin-5-yl]oxylbenzoic acid (2e, YM-36117) showed a more potent inhibitory activity for the human enzyme than ONO-3805 with an IC50 value of 5.3 nM and a reduced rat prostatic dihydrotestosterone (DHT) concentration by oral administration. The synthesis and the structure-activity relationships of these indoline and aniline derivatives are presented.     

Application of rhodanine,fluorene and semicarbazide hydrochloride as new spectrophotometric reagents for quinones

New selective and sensitive Spectrophotometric methods for quinone determination are described. Quinone samples are treated with either methanolic solution of rhodanine, fluorene in ammoniacal media or aqueous semicarbazide hydrochloride solution. Semicarbazide is the most sensitive reagent for the determination of 1,4-benzoquinone, 1,4-naphthoquinone and 2-methyl-1,4-naphthoquinone. Quinones substituted with electron withdrawing groups are better determined using rhodanine. The average recovery is 99.1%, 98.7% and 99.2% using rhodanine, fluorene and semicarbazide as reagents, respectively.     

Tuning the Electrical and Optical Properties of Diketopyrrolopyrrole Complexes for Panchromatic Dye‐Sensitized Solar Cells

A series of metal‐free organic dyes that were bridged by a diketopyrrolopyrrole moiety and were composed of indoline and triphenylamine as donor groups and furan and benzene as conjugated spacer groups were designed and synthesized for use in dye‐sensitized solar cells (DSCs). The photophysical properties, electrochemical properties, and performance of the DSCs were related to the structure of their corresponding dyes. Their absorption spectra broadened upon the introduction of the indoline and heterocyclic furan moieties through fine‐tuning of their molecular configuration. The overall conversion efficiencies of DSCs that were based on these dyes ranged from 5.14–6.53 %. Among the four dyes that were tested, indoline‐based ID01 and ID02 showed higher efficiencies (6.35 % and 6.53 %) as a result of their improved light‐harvesting efficiency and larger electron driving force. The ID01 dye, which contained an indoline moiety as an electron donor and a furan group as a π‐conjugated linker, showed an excellent monochromatic incident‐photon‐to‐current‐conversion efficiency (IPCE) spectrum (350–650 nm) with a maximum value of 78 % in the high plateau region and an onset value close to 800 nm. Intensity‐modulated photovoltage spectroscopy (IMVS) and impedance spectroscopy (IS) revealed that dyes that contained benzene conjugation spacers suppressed the charge‐recombination rate more efficiently than dyes that contained furan spacers, thereby resulting in improved photovoltage.     

Investigation of the products of the reaction of epichlorohydrin with aromatic amines

The synthesis of 2-(hydroxymethyl)benz [g]indoline derivatives by heating N-acyl derivatives of 2-(chloromethyl)benz[g]indoline in dimethyl sulfoxide is described. 3,6-Dichloro-1,2,3,4-tetrahydrobenzo[h]quinoline, 5-chloroazirido[1,2-a]benz[g]indoline, and derivatives of 2-substituted 5-chlorobenz [g]indoline were synthesized.See [1] for communication XITranslated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1111–1116, August, 1972.     

The acid-catalyzed rearrangement of 1-N-allylindolines

Zinc chloride-catalyzed rearrangement of 1-N-allylindoline and 1-N-(2-methylallyl)indoline proceeds readily in refluxing xylene to give 7-allylindoline and 7-(2-methylallyl)indoline in 73% and 86% yields, respectively. The reaction of 1-N-2-butenylindoline and zinc chloride give rise to the mixture of 7-(1-methylallyl)indoline, 7-(cis- and trans-1-methyl-1-propenyl)indoline, and 7-(trans-2-butenyl)indoline. On the other hand, the similar reaction of 1-N-(3-methyl-2-butenyl)indoline with zinc chloride led to the formation of a mixture of 1,2,5,6-tetrahydro-4,4-dimethyl-4H-pyrrolo[3,2,1-ij]quinoline and 7-(3-methyl-2-butenyl)indoline.     

Application of indoline dyes attached with strongly electron-withdrawing carboxylated indan-1,3-dione analogues linked with a hexylthiophene ring to dye-sensitized solar cells

An indoline dye attached with a carboxylated indan-1,3-dione moiety linked with a hexylthiophene ring exhibited the highest conversion efficiency among six analogues and D205. This result comes from the bathochromic UV–vis absorption band, suitable energy levels, good stability for redox process, and sufficiently long excited-state lifetime.     

Asymmetric synthesis of a prostaglandin D2 receptor antagonist

An asymmetric synthesis was developed for the production of a prostaglandin D(2) receptor antagonist for the treatment of allergic rhinitis. The stereogenic center was set using asymmetric allylic alkylation chemistry, and the core of the structure was constructed via Pd-catalyzed N-cyclization/Heck methodology. The synthesis relies on a late stage indoline oxidation which does not racemize the product.     

Novel indoline dye tetrabutylammonium carboxylates attached with a methyl group on the cyclopentane ring for dye-sensitized solar cells

(2R,3aR,8bR)- and (2S,3aS,8bS)-2-Methyl indoline dye tetrabutylammonium carboxylates exhibited the highest conversion efficiency among four regio and stereo isomers. These indoline dyes also showed higher conversion efficiency than DN350.