- Bromine-Substituted Fluorene: Molecular Structure, Br–Br Interactions, Room-Temperature Phosphorescence, and Tricolor Triboluminescence
-
Organic tribophosphorescence materials are rarely reported and the introduction of Br atoms may be a practical way to design such materials. Here four bromine-substituted fluorene-based derivatives are presented and BrFlu?CBr, having fluorescence-phosphorescence dual-emission induced not only by UV light but also by mechanical stimulus, manifests the highest phosphorescence efficiency of 4.56 % upon photoirradiation. During the grinding process, three different triboluminescent spectra were identified. Upon introduction of a mechanical stimulus, the triboluminescence emission is cyan, whereas after an extended period it changed to blue. After removing the mechanical stimulus, green-white phosphorescent emission was observed. Careful research on single-crystal structures and theoretical calculations demonstrate that strong Br???Br interactions are vital to facilitate spin-orbit coupling and promote intersystem crossing, thus generating the unique properties.
- Wang, Jiaqiang,Wang, Can,Gong, Yanbin,Liao, Qiuyan,Han, Mengmeng,Jiang, Tianjiao,Dang, Qianxi,Li, Yaqin,Li, Qianqian,Li, Zhen
-
-
Read Online
- Benzobisoxazole cruciforms: A tunable, cross-conjugated platform for the generation of deep blue OLED materials
-
Four new cross-conjugated small molecules based on a central benzo[1,2-d:4,5-d′]bisoxazole moiety possessing semi-independently tunable HOMO and LUMO levels were synthesized and the properties of these materials were evaluated experimentally and theoretically. The molecules were thermally stable with 5% weight loss occurring well above 350 °C. The cruciforms all exhibited blue emission in solution ranging from 433-450 nm. Host-guest OLEDs fabricated from various concentrations of these materials using the small molecule host 4,4′-bis(9-carbazolyl)-biphenyl (CBP) exhibited deep blue-emission with Commission Internationale de L'Eclairage (CIE) coordinates of (0.15 ≤ x ≤ 0.17, 0.05 ≤ y ≤ 0.11), and maximum luminance efficiencies as high as ~2 cd A-1. These results demonstrate the potential of benzobisoxazole cruciforms as emitters for developing high-performance deep blue OLEDs.
- Chavez, Ramiro,Cai, Min,Tlach, Brian,Wheeler, David L.,Kaudal, Rajiv,Tsyrenova, Ayuna,Tomlinson, Aimée L.,Shinar, Ruth,Shinar, Joseph,Jeffries-El, Malika
-
-
Read Online
- Highly luminescent network films from electrochemical deposition of peripheral carbazole functionalized fluorene oligomer and their applications for light-emitting diodes
-
Highly luminescent network films on flat indium tin oxide (ITO) substrates are prepared by electropolymerization using an electroactive and fluorescent compound as precursor; the LEDs prepared using these films as a light emitting layer achieve the maximum luminance and external quantum efficiency of 4224 cd/m2 and 0.72%, respectively, which demonstrates that electrochemical synthesis can be a new route to construct the highly luminescent films. ; The Royal Society of Chemistry 2006.
- Li, Mao,Tang, Shi,Shen, Fangzhong,Liu, Meirong,Xie, Weijie,Xia, Hong,Liu, Linlin,Tian, Leilei,Xie, Zengqi,Lu, Ping,Hanif, Muddasir,Lu, Dan,Cheng, Gang,Ma, Yuguang
-
-
Read Online
- Synthesis and fluorescent properties of conjugated copolymers containing maleimide and fluorene units at the main chain
-
Yamamoto or Suzuki-Miyaura coupling polymerizations of 2,3-diiodo-N- cyclohexylmaleimide with fluorene derivatives (2,7-dibromo-9,9′- dihexylfluorene and 9,9′-dihexylfluorene-2,7-diboronic acid) were carried out. The number-average molecular weights (Mn) of the resulting copolymers were 2600-3500 by gel permeation chromatography analysis. The fluorescence emission of the alternating copolymer showed the emission maxima at 551 nm in THF. On the other hand, the random copolymers showed the bimodal emission peaks at 418-420 and 555-557 nm region, respectively. The fluorescence peaks of the random copolymers on the long wavelength region (555-557 nm) were attributed to the conjugated neighboring N-cyclohexylmaleimide-9,9′- dihexylfluorene units in the polymer main chain. Furthermore, the copolymers exhibited the fluorescence solvatochromism by the difference of the polarity of solvents. The alternating and random copolymers showed the different fluorescence solvatochromism, and the emission colors are distinguishable by the naked eye, respectively. Copyright
- Nakamura, Munetoshi,Yamabuki, Kazuhiro,Oishi, Tsutomu,Onimura, Kenjiro
-
-
Read Online
- Electropolymerized AIE-active polymer film with high quantum efficiency and its application in OLED
-
A carbazole functionalized electro-active AIE-activity molecule, TPE-DFCz, was designed, synthesized, and well characterized. The clear difference in oxidation potentials between tetraphenylethylene (TPE) unit and carbazole groups was found which guaranteed that polymerization occurred only at the peripheral carbazole groups and the TPE unit remained unchanged. Its luminescent network film was prepared conveniently by electrochemical polymerization (EP). The cross-linked film exhibited green emission with high quantum efficiency of 63%, relatively smooth surface, and good thermal stability. The effect of different scan cycles on the optical property was also investigated. The electroluminescent device using the optimized polymer film as active layer showed a maximum luminance of 3200 cd?m?2 and a maximum luminance efficiency of 1.16 cd?A?1 with very low roll-off of the efficiency. The AIE-active EP films afford more opportunities to develop polymer films with high quantum efficiency via a simple, effective method and promote the potential applications in display devices.
- Li, Jinyu,Han, Xiao,Bai, Qing,Shan, Tong,Lu, Ping,Ma, Yuguang
-
-
Read Online
- Simple and efficient method for obtaining fluorene and spirobifluorene bromide derivatives
-
A mild, simple, and efficient synthetic procedure for the preparation of 2-monobromo-, 2,7-dibromo-, and 2,2′,7,7′-tetrabromo-substituted spirobifluorene derivatives and their key intermediates, 2-monobromo- and 2,7-dibromo-substituted fluorene compounds, has been developed. The oxidative bromination of fluorene and spirobifluorene was achieved using NaBr/H2O2 as the bromine source. High conversion of the starting materials was achieved together with good selectivities under optimized reaction conditions. Copyright Taylor & Francis Group, LLC.
- Jiang, Wen-Feng,Wang, Hui-Long,Wang, An-Gang,Li, Zhe-Qi
-
-
Read Online
- A novel amorphous oligo(phenylenevinylene) dimer with a biphenyl linkage center and fluorene end groups for electroluminescent devices
-
A new type of oligo(phenylenevinylene) dimer, 2,5,2,5- tetra(9,9-dihexylfluorenyl)biphenyl (TFB), with a biphenyl linkage center and four fluorene end groups, has been synthesized by the Wittig reaction. The full characterization of its structure and optical properties, as well as the performance of its electroluminescent devices are presented. TFB shows strong blue fluorescence both in solution and as a solid film. High-quality films of TFB for light-emitting devices (LEDs) can be fabricated both by vacuum evaporation and the spin-coating technique, which is very special and interesting. Single-layer and multi-layer light-emitting devices using TFB as the active layer all show efficient blue emission.
- He, Feng,Xia, Hong,Tang, Shi,Duan, Yu,Zeng, Ming,Liu, Linlin,Li, Mao,Zhang, Haiquan,Yang, Bing,Ma, Yuguang,Liu, Shiyong,Shen, Jiacong
-
-
Read Online
- Fluorene-based boronic acids as fluorescent chemosensor for monosaccharides at physiological pH
-
Two fluorene-based boronic acids, 9,9-dimethyl-9H-fluoren-2-yl-2-boronic acid (1) and 9,9-dimethyl-9H-fluoren-2,7-diyl-2,7-diboronic acid (2), were synthesized and their sensing abilities for detection of D-monosaccharides were investigated by fluorescence at physiological pH. It was found that both boronic acids 1 and 2 have high selectivity and sensitivity for D-fructose with stability constant of 47.2 and 412.9, respectively. The sensor 2 showed a linear response toward D-fructose in the concentration range from 5 × 10-5 to 10-1 mol L-1 with the detection limit of 2 × 10-5 mol L-1.
- Hosseinzadeh, Rahman,Mohadjerani, Maryam,Pooryousef, Mona
-
-
Read Online
- Synthesis and photovoltaic properties of conjugated copolymers bearing bis(9,9-di(2-ethylhexyl)-9H-fluoren-2-yl)quinoxaline subunit with deep HOMO level
-
A series of alternating copolymers (PT-BDFQx, PC-BDFQx and PBDT-BDFQx) have been synthesized bearing novel planar bis(9,9-di(2-ethylhexyl)-9H-fluoren-2-yl)quinoxaline (BDFQx) as acceptor unit, using benzo[1,2-b:4,5-b′]dithiophene (BDT), thiophene (T) and carbazole (C) as donor units via Stille or Suzuki coupling reactions. XRD characterization indicated that the presence of planar BDFQx unit (monomer 8) is favorable for the promotion of crystallization in the solid state and GPC results illustrated that the import of multiple chains in planar BDFQx unit raises the polymers molecular weight. Electrochemical measurement results suggested that three copolymers possess deep HOMO energy level of -5.50-5.77 eV. The polymer solar cell with structure of ITO/PEDOT:PSS (30 nm)/polymer: PCBM (60 nm)/Bphen (10 nm)/Ag (100 nm) exhibited the highest Voc of 0.80 V with PBDT-BDFQx as p-type polymer, while the best power conversion efficiency (PCE) of 0.9% was obtained using a blend of PBDT-BDFQx and PCBM(1:4) as active layer.
- Chen, Jing,Deng, Xianping,Yang, Daobin,Huo, Erfu,Chen, Yunqing,Huang, Yan,Lu, Zhiyun
-
-
Read Online
- Ligand Engineering for the Efficient Dye-Sensitized Solar Cells with Ruthenium Sensitizers and Cobalt Electrolytes
-
Over the past 20 years, ruthenium(II)-based dyes have played a pivotal role in turning dye-sensitized solar cells (DSCs) into a mature technology for the third generation of photovoltaics. However, the classic I3-/I- redox couple limits the performance and application of this technique. Simply replacing the iodine-based redox couple by new types like cobalt(3+/2+) complexes was not successful because of the poor compatibility between the ruthenium(II) sensitizer and the cobalt redox species. To address this problem and achieve higher power conversion efficiencies (PCEs), we introduce here six new cyclometalated ruthenium(II)-based dyes developed through ligand engineering. We tested DSCs employing these ruthenium(II) complexes and achieved PCEs of up to 9.4% using cobalt(3+/2+)-based electrolytes, which is the record efficiency to date featuring a ruthenium-based dye. In view of the complicated liquid DSC system, the disagreement found between different characterizations enlightens us about the importance of the sensitizer loading on TiO2, which is a subtle but equally important factor in the electronic properties of the sensitizers.
- Aghazada, Sadig,Gao, Peng,Yella, Aswani,Marotta, Gabriele,Moehl, Thomas,Teuscher, Jo?l,Moser, Jacques-E.,De Angelis, Filippo,Gr?tzel, Michael,Nazeeruddin, Mohammad Khaja
-
-
Read Online
- Conjugated diene monomer 9-9 - dialkyl fluorene as structural unit and synthesis method thereof
-
The invention relates to a conjugated diene monomer 9-9 - dialkyl fluorene as a structural unit and a synthesis method thereof, and belongs to the technical field of organic synthesis. 9, 9 - Dialkyl fluorene is the structural unit of the conjugated diene monomer. Herein R is a linear or branched alkyl group having a different number (6 - 30) of carbon atoms, n Shows functional groups of each intermediate, and a functional ethylenic monomer with Suzuki and 9 dialkyl fluorene as a core with different conjugation lengths can be obtained by repeating the bromination and acetylation reduction of the fluorene or 9 - fluorene oligomer. The problem of flexible expansion of chemical reaction of organic small molecules of fluorene units can be solved.
- -
-
Paragraph 0042; 0045-0049
(2021/10/05)
-
- Fluorene derivative with AIE characteristic, preparation method and application
-
The invention discloses a fluorene derivative with AIE characteristic. The structural formula of the derivative is shown in the specification. In the formula, R =- CHO, -COOH, -Br, -I, -NO2, -NH2, -OCH3, -CH3, -CN, -NHCOCH3, -CF3 or -CCl3. The fluorene derivative can be used as a fluorescent probe for identifying small biological molecules, has efficient specific identification on tryptophan (the detection limit is 1.15 [mu]M), and can also be used for detecting small molecular substances such as explosives, anions, metal cations (including rare earth metals) and the like.
- -
-
Paragraph 0015
(2021/09/04)
-
- Solid-state construction of zigzag periphery: Via intramolecular C-H insertion induced by alumina-mediated C-F activation
-
Caryl-F bond activation has become an important and quickly developing method for construction of carbon-based materials. We report that alumina-mediated C-F bond activation (AmCFA) enables construction of PAHs with zigzag periphery. This method includes
- Akhmetov, Vladimir,Amsharov, Konstantin,F?rtsch, Andreas,Feofanov, Mikhail
-
supporting information
p. 12325 - 12328
(2021/11/30)
-
- Bipolar micromolecule luminescent material processed by using environment-friendly solvent as nucleus and preparation method and application thereof
-
The invention discloses a bipolar small molecular luminescent material capable of being processed by adopting an environment-friendly solvent and taking a naphtho-indenofluorene unit as a core as well as a production method and application of the bipolar small molecular luminescent material. The production method comprises the following steps: by taking the naphtho-indenofluorene unit containing a polar substituent group as the core; carrying out a Suzuki coupling reaction, and connecting an electron donor unit and an electron withdrawing unit onto two sides of the naphtho-indenofluorene unit in sequence, so as to obtain the bipolar small molecular luminescent material taking the naphtho-indenofluorene unit as the core. The bipolar small molecular luminescent material taking the naphtho-indenofluorene unit as the core, disclosed by the invention, has good solubility, film forming property and thin film form stability in the environment-friendly solvent; a luminescent layer produced by the luminescent material can avoid a mixing phenomenon with a hole/electron transmission layer interface; the prepared luminescent layer does not need to be subjected to annealing treatment when being used for preparing a luminescent device, so that a preparation process is simple.
- -
-
Paragraph 0038-0041
(2020/05/08)
-
- Spirooxazine photochromic compound and preparation method thereof
-
The invention discloses a spirooxazine photochromic compound and a preparation method thereof, and belongs to the technical field of organic functional materials. The molecular structure is disclosedin the invention, whereinR1 and R2 are hydrogen, C1-C6 alkyl (CH2, m = 1, 2, 3, 4, 5, 6), and benzyl; R3and R4 are hydrogen, halogen, C1-C6 alkyl (CH2, m = 1, 2, 3, 4, 5, 6). Accordingto the invention, a photothermal stable fluorene phenol structure is introduced; different groups are used for substitution; the advantages of a novel photochromic material with spirooxazine are provided; the light response speed is high; meanwhile, color fading is rapid, moreover, the photo-thermal stability is good, an open-loop state and a closed-loop state can stably exist for a long time; guidance is provided for solving the problem that the ring-opening state ofspirooxazine photochromic compounds is unstable; the photochromic compound with various color changes from colorless to red, yellow, green, blue or purple is realized, the color variety of color change is richer, the market diversification requirements are finally met, the synthesis raw materials are cheap and easily available, and the synthesis process is easy to realize industrialization.
- -
-
Paragraph 0016; 0018; 0020
(2020/06/17)
-
- A high-purity 2 - bromofluorene preparation method
-
A preparation method of highly pure 2-bromofluorene belongs to the technical field of synthesis of organic matters. The 2-bromofluorene is prepared from 2-aminofluorene and hydrobromic acid. The preparation method comprises the following steps: placing the hydrobromic acid and the 2-aminofluorene in a reactor, stirring the above raw materials, heating the raw materials, carrying out a refluxing reaction for 2-3 h, cooling the obtained reaction product to 40-60 DEG C, adding a cuprous compound, uniformly stirring the cuprous compound and the cooled reaction product, dropwise adding a nitrous acid compound, carrying out a heat insulation reaction for 1-2 h after the dropwise addition is finished, adding toluene to dissolve the obtained heat insulation reaection product, and carrying out filtration desalting, liquid separation, water washing and organic layer concentration to obtain the 2-bromofluorene. The preparation method has the advantages of simplicity, mild and stable reaction product, realization of direct obtaining of the 2-bromofluorene through a one-pot technology, and high yield and high purity of the obtained 2-bromofluorene.
- -
-
Paragraph 0028-0039
(2019/06/26)
-
- Preparation method of key intermediate of anti-hepatitis C drug ledipasvir
-
The invention provides a preparation method of a key intermediate 1-(7-bromo-9,9-difluoro-9H-fluoren-2-yl)-2-chloroethanone. The method comprises the steps as follows: 2-amino-5-bromobenzoic acid is taken as a raw material, and subjected to diazotization, iodination,synthesis of 5-bromo-2-iodobenzoic acid, methylation, coupling reaction with phenylboronic acid, ester hydrolysis, acyl chlorination,intramolecular Friedel-Crafts alkylation, carbonyl reduction, iodization, fluorination and final reaction with 2-chloro-N-methoxy-N-methylacetamide to prepare the target product. The process adopts easily available starting raw materials, is low in price and free of hazardous process and has mild reaction conditions..
- -
-
-
- Synthesis method of 2-bromobenzonitrile
-
The invention discloses a synthesis method of 2-bromobenzonitrile, which comprises the following steps of: mixing fluorene with hydrobromic acid, dibromide tribenzylamine and a catalyst, heating and refluxing for 1-1.5h, cooling to 25-35 DEG C, adding dibromohydantoins, stirring uniformly, keeping the temperature for 3-5h, standing the reaction solution, carrying out separation of the water phaseand the organic phase, washing the organic phase, drying, filtering, concentrating, and recrystallizing to obtain 2-bromobenzonitrile. The production rate and purity of 2-bromobenzonitrile are high, the reaction condition is mild, the operation is simple, the operation time is less, the industrial production is realized, the utilization rate of the raw materials is high, and the environment is green and environment-friendly.
- -
-
Paragraph 0021-0042
(2018/10/26)
-
- Anti-hepatitis c pharmaceutical intermediates
-
The invention provided a compound represented by the formula I and a method utilizing the compound to prepare an anti hepatitis C drug. The preparation method is simple and economic, and is capable of being applying to industrial production, so the preparation of an anti hepatitis C drug may be achieved. The formula I is represented in the description, wherein the R represents fluorine or hydrogen, and the n is equal to 2 or 3.
- -
-
Paragraph 0067; 0068
(2018/04/03)
-
- Carbocation Catalyzed Bromination of Alkyl Arenes, a Chemoselective sp3 vs. sp2 C?H functionalization.
-
The versatility of the trityl cation (TrBF4) as a highly efficient Lewis acid organocatalyst is demonstrated in a light induced benzylic brominaion of alkyl-arenes under mild conditions. The reaction was conducted at ambient temperature under common hood light (55 W fluorescent light) with catalyst loadings down to 2.0 mol% using N-bromosuccinimide (NBS) as the brominating agent. The protocol is applicable to an extensive number of substrates to give benzyl bromides in good to excellent yields. In contrast to most previously reported strategies, this protocol does not require any radical initiator or extensive heating. For electron-rich alkyl-arenes, the trityl ion catalyzed bromination could be easily switched between benzylic sp3 C?H functionalization and arene sp2 C?H functionalization by simply alternating the solvent. This chemoselective switch allows for high substrate control and easy preparation of benzyl bromides and bromoarenes, respectively. The chemoselective switch was also applied in a one-pot reaction of 1-methylnaphthalene for direct introduction of both sp3 C?Br and sp2 C?Br functionality. (Figure presented.).
- Ni, Shengjun,El Remaily, Mahmoud Abd El Aleem Ali Ali,Franzén, Johan
-
supporting information
p. 4197 - 4204
(2018/09/25)
-
- Design and synthesis of solution processable green fluorescent D-π-A dyads for OLED applications
-
New solution processable organic donor-π-acceptor dyads 1 and 2 having electron donating phenoxazine and electron accepting oxadiazole groups have been synthesized. Intramolecular electron communication between the donor and acceptor moieties of these dyads was tuned through changing the substitution pattern at the phenylene linker. The photophysical properties of these dyads have been studied in the solution and film states. These dyads showed green fluorescence and exhibited a positive solvatochromism in the emission spectra, which indicates more polar excited states owing to an efficient charge migration from the donor phenoxazine to the acceptor oxadiazole moiety. The electrochemical, morphological and thermal properties were investigated through cyclic voltammetry, thermogravimetric and atomic force microscopy (AFM) analyses. To understand the electronic structure and band gap of these dyads, density functional theory (DFT) calculations have been performed. Furthermore, we have fabricated the solution processed un-doped electroluminescence devices based on these dyads, which exhibited efficient green emission with Commission Internationale de l'Eclairage (CIE) coordinates of (0.26, 0.49) and (0.27, 0.47) for 1 and 2, respectively, with a luminance maximum of ca. 1751 cd m-2 for the dyad 1, thereby demonstrating its use in organic light emitting diodes (OLEDS).
- Thurakkal, Shameel,Sanju, Krishnankutty S.,Soman, Anjaly,Unni, K. N. Narayanan,Joseph, Joshy,Ramaiah, Danaboyina
-
p. 5456 - 5464
(2018/04/02)
-
- Design and synthesis of N-substituted perylene diimide based low band gap polymers for organic solar cell applications
-
In this study, we report on the synthesis and device studies of a series of new copolymers containing N-substituted perylene dimide and dioctylfluorene units as part of the main backbone. A facile synthetic approach avoiding non-selective bromination was used to synthesize the monomer M1 by the reaction of perylene-3,4,9,10-tetracarboxylic dianhydride with 2-amino-7-bromo-9,9-dioctylfluorene. The copolymers P1 and P2 were synthesized by Suzuki polycondensation of M1 with 2,2′-(9,9-dioctyl-9H-fluoren-2,7-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) M2 and 9-(heptadecan-9-yl)-2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole M3, respectively. The copolymer P3 was synthesized by direct arylation polymerization of M1 with 4,7-bis(4-octylthiophen-2-yl)benzo[c]-1,2,5-thiadiazole M4. All the copolymers showed thermal stability greater than 380 °C as evidenced from thermogravimetric analysis. The copolymers exhibited a narrow optical band gap (1.80-2.08 eV) with their UV-visible absorption spectra extending up to the NIR region and they are found to be suitable for use in OSC applications. The molecular weights of the polymers P1-P3 were found to be in the range of 10.68 to 16.02 kg mol-1 as measured from GPC analysis. The surface morphology of the active layers based on P1/P2/P3:P3HT blend films was investigated by AFM and the rms values from height images range from 0.65 to 2.90 nm. The polymers were blended with P3HT to fabricate BHJ solar cells in three different weight ratios i.e. 1 : 1, 1.5 : 1 and 2 : 1 and the best power conversion efficiency was observed for the binary film of P3:P3HT blend device in a 1 : 1 weight ratio which reached up to 1.96% with a Voc of 0.55 V, Jsc of 10.12 mA cm-2 and FF of 34.63% which is among the highest reported for BHJ solar cells with N-substituted PDI based acceptors.
- Meena, Savita,Mohammad, Tauheed,Dutta, Viresh,Jacob, Josemon
-
p. 30468 - 30480
(2018/09/11)
-
- Ledipasvir key intermediate and preparation method thereof
-
The invention discloses a ledipasvir key intermediate LD-J, a structure of the ledipasvir key intermediate LD-J and a preparation method of the ledipasvir key intermediate LD-J. The preparation methodcomprises the following steps: (A1) preparing LD-G; (A2) preparing LD-H; (A3) preparing LD-I; (A4) preparing a Grignard reagent; and (A5) preparing LD-J. The ledipasvir key intermediate LD-J and thepreparation method thereof have the advantages that the process is mature and stable, the product is stable in quality, the production process is safe and reliable, and the preparation method is suitable for industrial production.
- -
-
Paragraph 0026-0031; 0053; 0074
(2018/04/26)
-
- Ledipasvir preparation method
-
The invention discloses a Ledipasvir preparation method. The Ledipasvir preparation method includes steps: (1) Ledipasvir intermediate product 1-LD-B preparation; (2) Ledipasvir intermediate product 2-LD-E preparation; (3) Ledipasvir intermediate product 3-LD-F preparation; (4) Ledipasvir intermediate product 4-LD-J preparation; (5) Ledipasvir intermediate product 5-LD-L preparation; (6) Ledipasvir-LD-Q preparation. The Ledipasvir preparation method has advantages of technical maturity and stability, product quality stability, safety and reliability in production process and suitableness for industrial production.
- -
-
Paragraph 0097; 0099; 0100; 0165; 0170; 0239
(2018/05/16)
-
- Preparation method of Ledipasvir key intermediate
-
The invention provides a preparation method of a Ledipasvir key intermediate 7-bromo-2-(chloracetyl)-9,9-difluorofluorene. 4-bromaniline is used as an initial raw material, by virtue of aminoacetylation and benzyl-chlorophene alkylation, acetyl in the concentrated hydrochloric acid is removed, the diazotization coupling is performed under the catalysis of copper to obtain 2-bromofluorene, then the2-bromofluorene and a fluorine reagent react to obtain 7-bromo-9,9-difluorofluorene, finally the 7-bromo-9,9-difluorofluorene has Friedel-Crafts acylation reaction with chloroacetyl chloride to obtain an intermediate 7-bromo-2-(chloracetyl)-9,9-difluorofluorene. The preparation method of the invention is short in synthetic route, safe in process, simple and convenient in operation, low in raw material cost and capable of meeting the industrialized production requirement.
- -
-
Paragraph 0041; 0046; 0049; 0054; 0057; 0062; 0066
(2019/01/16)
-
- A 2 - bromofluorene derivative synthesis method
-
The invention provides a synthetic method for 2-bromofluorene derivatives. The synthetic method includes the following steps: hybrid reaction of fluorene or derivatives thereof, quaternary ammonium salt, sodium bromate and hydrobromic acid is carried out; extraction is performed through dichloromethane to obtain organic phase; then the organic phase is washed, dried, filtered and concentrated through anhydrous sodium sulfate, and finally, recrystallization is performed, and 2-bromofluorene derivatives disclosed by the invention can be obtained. The synthetic method for 2-bromofluorene derivatives, provided by the invention has the advantages that the operation method is simple, required equipment for reaction is simple, the reaction condition is gentle, and the conversion efficiency is high; the defects in the conventional synthetic method for 2-bromofluorene derivatives that the conversion efficiency is low, the reaction is complicated and the reaction efficiency is low are avoided.
- -
-
Paragraph 0020-0026; 0029-0037; 0048-0065
(2017/08/25)
-
- Blue oligomer based on dibenzothiophene-S,S-dioxide unit and preparation method and application of blue oligomer
-
The invention discloses a blue oligomer based on a dibenzothiophene-S,S-dioxide unit and a preparation method and application of the blue oligomer. The blue oligomer is mainly characterized by comprising a fluorene structure unit and the dibenzothiophene-S,S-dioxide structure unit. The preparation method mainly comprises the step of preparation of the blue oligomer based on the dibenzothiophene-S,S-dioxide unit. Due to the fact that the electroluminescence efficiency and the spectral stability are improved by introducing the dibenzothiophene-S,S-dioxide structure unit into the oligomer, the novel oligomer blue-light emitting material is obtained. According to the obtained blue oligomer based on the dibenzothiophene-S,S-dioxide unit, an electroluminescence device prepared through film formation of a solution processing method is high in efficiency, good in spectral stability and suitable for being adopted as a light-emitting layer of a light-emitting diode and a flat-panel displayer.
- -
-
Paragraph 0057; 0058; 0059; 0060
(2017/03/08)
-
- Bipolar small-molecule luminescent material adopting aromatic heterocyclicindenofluorene unit as core as well as preparation method and application of bipolar small-molecule luminescent material
-
The invention discloses a bipolar small-molecule luminescent materialadopting an aromatic heterocyclicindenofluorene unit as a core as well as a preparation method and an application of the bipolar small-molecule luminescent material. The bipolar small-molecule luminescent material adopting the aromatic heterocyclicindenofluorene unit as the core is prepared through a Suzuki polymerization reaction, the synthetic method is simple, purification is easy, and industrial application is facilitated. The bipolar small-molecule luminescent material adopting the aromatic heterocyclicindenofluorene unit as the core is better in aromatic heterocyclicindenofluorene planarity and has higher fluorescence quantum yield; meanwhile, the bipolar small-molecule luminescent material adopting the aromatic heterocyclicindenofluorene unit as the core has good solubility, film-forming property and film morphology stability, is suitable for solution processing and printing display and is used for preparation of a luminescent layer of an organic light emitting diode, and annealing treatment is not needed when the luminescent layer based on the bipolar small-molecule luminescent material is used for preparing a device, so that the preparation process is simple.
- -
-
Paragraph 0046; 0047; 0048; 0049
(2017/08/19)
-
- One on the basis of [...]high fused ring of [6] spiral alkene compound and its synthesis method
-
The invention provides a kind of highly condensed ring [6]helicene compounds (I) based on fluorene and naphthalene and synthetic method thereof, and belongs to the technical field of chemical engineering. The highly condensed ring [6]helicene compounds with photoelectric functions are successfully prepared by taking naphthalene and fluorene derivatives as raw materials and employing a photocatalytic cyclization method. The synthetic method has the advantages of high yield, short time, simple operation and the like, also employs common cheap reagents, helps to reduce preparation cost, and is easy for popularization and application. The highly condensed ring [6]helicene compounds based on fluorene and naphthalene has extremely good solubility in different organic solvents, and are beneficial for purification and film making. Multiple highly condensed ring [6]helicene compounds can be obtained by introducing different substitutes. The highly condensed ring [6]helicene compounds based on fluorene and naphthalene is hopeful to be widely applied to fields such as organic electroluminescence, Organic field effect transistor, organic second-order nonlinear or chiral liquid crystal, biological medicines and the like.
- -
-
Paragraph 0065; 0066; 0067
(2017/09/02)
-
- Regioselective monobromination of aromatics via a halogen bond acceptor-donor interaction of catalytic thioamide and N-bromosuccinimide
-
Regioselective monobromination of various aromatics was achieved at room temperature using N-bromosuccinimide and 5 mol% of thioamides in acetonitrile. With thiourea as catalyst, activated aromatics, such as anisole, acetanilide, benzamide and phenol analogues containing electron donating or withdrawing groups, were brominated with high regioselectivity. Room temperature brominations of weakly activated aromatics and deactivated 9-fluorenone were accomplished by 5 mol% thioacetamide, higher substrates concentrations and longer reaction times. A backbonding of the bromine lone pairs with the π*of C[dbnd]S group and a halogen bond between the halogen bond donor bromine and the halogen bond acceptor sulfur of the thioamide are thought to be the principal interactions and cause of N-bromosuccinimide activation.
- Bovonsombat, Pakorn,Teecomegaet, Pattaradra,Kulvaranon, Panisanun,Pandey, Aditi,Chobtumskul, Kittithorn,Tungsirisurp, Sireethorn,Sophanpanichkul, Punyanuch,Losuwanakul, Satreerat,Soimaneewan, Dechathon,Kanjanwongpaisan, Patcharida,Siricharoensang, Pornpawit,Choosakoonkriang, Sirirat
-
p. 6564 - 6572
(2017/10/17)
-
- Synthesis and properties of dicarbazolyltriphenylethylene-substituted fluorene derivatives exhibiting aggregation-induced emission enhancement
-
Two novel dicarbazolyltriphenylethylene-substituted fluorene derivatives DctF and Dct2F were synthesized by the Wittig-Horner and Suzuki coupling reactions. It was reasoned that introducing linear alkyl chains into the fluorene structure could facilitate the deposition of high-quality films by an economical and simple process. The thin solid films of DctF and Dct2F show strongly enhanced emissions in comparison to their dilute solutions, which indicate the aggregation-induced emission enhancement (AIEE). Their decomposition temperatures (Td) exceed 400°C and the glass transition temperature (Tg) of DctF is 105°C. The maximum fluorescence emission wavelengths are in the region of 458-469 nm.
- Zhang, Qiang,Huang, Tian,He, Xing,Zhao, Zhuo-Ran,Zhao, Xin
-
-
- Molecular Engineering of UV/Vis Light-Emitting Diode (LED)-Sensitive Donor–π–Acceptor-Type Sulfonium Salt Photoacid Generators: Design, Synthesis, and Study of Photochemical and Photophysical Properties
-
A series of donor–π–acceptor-type sulfonium salt photoacid generators (PAGs) were designed and synthesized by systematically changing electron-donating groups, π-conjugated systems, electron-withdrawing groups, and the number of branches through molecular engineering. These PAGs can effectively decompose under UV/Vis irradiation from a light-emitting diode (LED) light source because of the matching absorption and emitting spectra of the LEDs. The absorption and acid-generation properties of these sulfonium salts were elucidated by UV/Vis spectroscopy and so forth. Results indicated that the PAG performance benefited from the introduction of strong electron-donating groups, specific π-conjugated structures, certain electron-withdrawing groups, or two-branched structures. Most sulfonium salts showed potential as photoinitiators under irradiation by a wide variety of UV and visible LEDs.
- Wu, Xingyu,Jin, Ming,Xie, Jianchao,Malval, Jean-Pierre,Wan, Decheng
-
supporting information
p. 15783 - 15789
(2017/10/20)
-
- Bipolar micromolecular luminescent material based on 4-(9H-carbazole-9-yl) aniline and preparation method and application thereof
-
The invention discloses a bipolar micromolecular luminescent material based on 4-(9H-carbazole-9-yl) aniline and a preparation method and application thereof. The material is mainly characterized in that the 4-(9H-carbazole-9-yl) aniline is used as a hole transport center unit, and bipolar micromolecules with the 4-(9H-carbazole-9-yl) aniline as the center are obtained by selecting groups with an electron transmission function. The bipolar micromolecules prepared through the method can be used for making a luminescent layer of an organic light emitting diode.
- -
-
Paragraph 0055; 0056; 0057; 0058
(2016/10/09)
-
- Naphthoindenofluorene unit-containing micromolecule luminescent material processed through eco-friendly solvent and its preparation method and use
-
The invention discloses a naphthoindenofluorene unit-containing micromolecule luminescent material processed through an eco-friendly solvent and its preparation method and use. The micromolecule luminescent material utilizes naphthoindenofluorene as a core unit. Through use of a group with an electron transmission unit, a micromolecule material with naphthoindenofluorene as a core is obtained. The naphthoindenofluorene unit-containing micromolecule luminescent material can be processed through an eco-friendly solvent. The prepared micromolecule material can be used for preparation of an organic light-emitting diode luminescent layer.
- -
-
Paragraph 0043; 0044; 0045
(2017/01/19)
-
- Tuning two-photon absorption cross-sections for triphenylamine derivatives
-
A methylene bridge link connecting the ortho-positions within the triphenylamine scaffold increases the molecular planarity significantly. The one-photon spectroscopies of bridged triphenylamine molecules show considerable extended conjugation relative to their triphenylamine counterparts, leading to enhanced two-photon absorption (TPA) cross-sections. Various substituents at the scaffold have been prepared and studied. Using a femtosecond laser source Z-scan method, the TPA cross-sections were characterized. The maximum magnitude of the TPA cross-section is ~4800 GM, which is four times that of its triphenylamine counterpart. The Royal Society of Chemistry.
- Fang, Zhen,Webster, Richard D.,Samoc, Marek,Lai, Yee-Hing
-
p. 17914 - 17917
(2013/10/01)
-
- Molecular engineering of organic sensitizers with planar bridging units for efficient dye-sensitized solar cells
-
Here comes the sun: Three highly efficient organic sensitizers with sterically hindered fluorenyl units and planar indenothiophene derivatives were designed and synthesized (see figure). Devices based on one of these compounds, JK-303, gave overall conversion efficiencies of 8.69, 9.04, 7.27, and 5.82 % using I-/I3-, CoII/CoIII, polymer gel, and solid-state electrolytes, respectively. These efficiencies are some of the highest reported for DSSCs based on organic sensitizers. Copyright
- Lim, Kimin,Ju, Myung Jong,Na, Jongbeom,Choi, Hyeju,Song, Min Young,Kim, Byeonggwan,Song, Kihyung,Yu, Jong-Sung,Kim, Eunkyoung,Ko, Jaejung
-
supporting information
p. 9442 - 9446
(2013/07/26)
-
- Blue-light-emitting multifunctional triphenylamine-centered starburst quinolines: Synthesis, electrochemical and photophysical properties
-
A series of triphenylamine-centered starburst quinolines (1a-1g) have been synthesized by Friedlaender condensation of the 4,4′,4′′- triacetyltriphenylamine (2) and 2-aminophenyl ketones (3a-3g) in the presence of catalytic sulfuric acid and characterized well. They are thermally robust with high glass transition temperatures (above 176.4 °C) and decomposition temperatures (above 406 °C). These compounds emit blue fluorescence with λEmmax ranging from 433 to 446 nm in dilute toluene solution and 461 to 502 nm in the solid-state and have a relatively high efficiency (Φu = 0.98-0.57). 1a-1g have estimated ionization potentials (IP) of 4.54 to 6.45 eV which are significantly near or higher than those of well-known electron transport materials (ETMs), including tris(8- hydroxyquinoline)aluminium (Alq3) (IP = 5.7-5.9 eV), and previously reported oligoquinolines (IP = 5.53-5.81 eV). Quantum chemical calculations using DFT B3LYP/6-31G* showed the highest occupied molecular orbital (HOMO) of -5.05 to -4.81 eV, which is close to the work function of indium tin oxide (ITO). These results demonstrate the potential of 1a-1g as hole-transporting/light-emitting/electron-transport materials and the host-materials of a dopant for hole-injecting for applications in organic light-emitting devices.
- Jiang, Peng,Zhao, Dong-Dong,Yang, Xiao-Li,Zhu, Xiao-Lin,Chang, Jin,Zhu, Hong-Jun
-
scheme or table
p. 4704 - 4711
(2012/08/08)
-
- Novel multifunctional organic semiconductor materials based on 4,8-substituted 1,5-naphthyridine: Synthesis, single crystal structures, opto-electrical properties and quantum chemistry calculation
-
A series of 4,8-substituted 1,5-naphthyridines (1a-1h) have been successfully synthesised by a Suzuki cross-coupling between 4,8-dibromo-1,5- naphthyridine (4) and the corresponding boronic acids (2a-2h) in the presence of catalytic palladium acetate in yields of 41.4-75.8% and have ben well characterized. They are thermally robust with high phase transition temperatures (above 186 °C). Compounds 1b, 1e and 1f crystallized in the monoclinic crystal system with the space groups P21/c, P21/c and P21/n, respectively. All of them show the lowest energy absorption bands (λmaxAbs: 294-320 nm), revealing low optical band gaps (2.77-3.79 eV). These materials emit blue fluorescence with λmaxEm ranging from 434-521 nm in dilute solution in dichloromethane and 400-501 nm in the solid state. 4,8-Substituted 1,5-naphthyridines 1a-1h have estimated electron affinities (EA) of (2.38-2.72 eV) suitable for electron-transport materials and ionization potentials (IP) of 4.85-5.04 eV facilitate excellent hole-injecting/hole-transport materials properties. Quantum chemical calculations using DFT B3LYP/6-31G* showed nearly identical the lowest unoccupied molecular orbitals (LUMO) of -2.39 to -2.19 eV and the highest occupied molecular orbitals (HOMO) of -5.33 to -6.84 eV. These results demonstrate the 4,8-substituted 1,5-naphthyridines 1a-1h with a simple architecture might be promising blue-emitting (or blue-green-emitting) materials, electron-transport materials and hole-injecting/hole-transport materials for applications for developing high-efficiency OLEDs.
- Wang, Kun-Yan,Chen, Chen,Liu, Jin-Fang,Wang, Qin,Chang, Jin,Zhu, Hong-Jun,Li, Chong
-
scheme or table
p. 6693 - 6704
(2012/09/22)
-
- NOVEL ORGANIC ELECTROLUMINESCENT COMPOUNDS AND ORGANIC ELECTROLUMINESCENT DEVICE USING THE SAME
-
Provided are novel organic electroluminescent compounds, and organic electroluminescent devices comprising the same. Since the organic electroluminescent compounds exhibit high luminous efficiency in blue color, and excellent life property of the material, they may be used to manufacture OLEDs having very good operation life.
- -
-
Page/Page column 19
(2011/09/30)
-
- Cyclometalated platinum(II) 6-phenyl-4-(9,9-dihexylfluoren-2-yl)-2, 2′-bipyridine complexes: Synthesis, photophysics, and nonlinear absorption
-
A series of mononuclear and dinuclear cyclometalated platinum(II) 6-phenyl-4-(9,9-dihexylfluoren-2-yl)-2,2′-bipyridine complexes (F-1-F-5) were synthesized and their photophysical properties were systematically investigated. All complexes exhibit strong 1π, π*absorption bands in the UV region, and a broad, structureless charge transfer band in the visible region. The charge-transfer band is broadened and red-shifted for F-3-F-5 compared to those for F-1 and F-2 because of the electron-donating acetylide ligand and the involvement of the ligand-to-ligand charge transfer character. The molar extinction coefficients for the dinuclear complex F-5 are much higher than those for the mononuclear complexes F-1-F-4, indicating the electronic coupling through the bridge ligand. All complexes are emissive in solution at room temperature and in glassy matrix at 77 K. When excited at the charge transfer absorption band, the complexes exhibit a long-lived red/orange emission around 600 nm, which is attributed to a triplet metal-to-ligand charge transfer/intraligand charge transfer emission ( 3MLCT/3ILCT). For emission at 77 K, the emitting state is tentatively assigned as 3MLCT for F-2-F-4, and 3MLCT/ 3π,π*for F-1 and F-5 taking into account the emission energy, the shape of the spectrum, the lifetime, and the thermally induced Stokes shift. F-1-F-4 exhibit broad triplet transient difference absorption in the visible to the near-IR region, with a lifetime comparable to those measured from the decay of the 3MLCT/3ILCT emission. Therefore, F-1-F-4 give rise to a strong reverse saturable absorption for ns laser pulses at 532 nm. Z-scan experiments were carried out at 532 nm using both ns and ps laser pulses, and the experimental data was fitted by a five-band model to extract the singlet and triplet excited-state absorption cross sections. The degree of reverse saturable absorption follows this trend: F-1 = F-2 > F-3 > F-4 > F-5, which is mainly determined by the ratio of the triplet excited-state absorption cross-section to that of the ground-state and the triplet excited-state quantum yield. Comparison of the photophysics of F-1, F-2, and F-3 to those of their corresponding Pt complexes without the fluorenyl substituent discovers that F-1-F-3 exhibit larger molar extinction coefficients for their low-energy charge transfer absorption band, longer triplet excited-state lifetimes, higher emission quantum yields, and increased ratios of the excited-state absorption cross-section to that of the ground-state.
- Shao, Pin,Li, Yunjing,Yi, Jing,Pritchett, Timothy M.,Sun, Wenfang
-
scheme or table
p. 4507 - 4517
(2010/07/04)
-
- Polyfluorene with p-carborane in the backbone
-
Polyfluorene with p-carborane in the backbone was synthesized from the new monomer 1,12-bis(7-bromo-9,9-dihexyl-9H-fluoren-2-yl)-closo-1,12- dicarbodecaborane to give a high MW, soluble, blue-emitting material characterized by NMR, UV-vis, and fluorescence spectroscopy.
- Peterson, Joseph J.,Simon, Yoan C.,Coughlin, E. Bryan,Carter, Kenneth R.
-
supporting information; experimental part
p. 4950 - 4952
(2010/01/06)
-
- 3,4-Bis(5-iodo-2-methylthien-3-yl)-2,5-dihydrothiophene: A powerful synthon for the preparation of photochromic dithienylethene derivatives
-
A dithienylethene synthon, 3,4-bis-(5-iodo-2-methylthien-3-yl)-2,5- dihydrothiophene, was prepared and used as a starting material for the preparation of several photochromic dithienylethene derivatives via Suzuki cross-coupling reactions. The dithienylethene synthon was stable once stored in the dark at room temperature. Georg Thieme Verlag Stuttgart.
- Xie, Nan,Zeng, De Xing,Chen, Yi
-
p. 737 - 740
(2007/10/03)
-
- Two-photon responsive chromophores containing electron accepting core units
-
Provided are chromophores of the formula Q—(—L—Z)x, wherein x is 2 or 3, wherein Q is selected from the group consisting of wherein L is wherein R is an alkyl group having 1 to 20 carbon atoms, and wherein Z is selected from the group consisting of
- -
-
Page column 5
(2010/02/06)
-
- Two-photon responsive chromophores containing electron accepting cores
-
Provided are chromophores of the formula Q—(—L—Z)x, wherein x is 3 or 4, wherein Q is selected from the group consisting of wherein L is selected from the group consisting of wherein R is an alkyl group having 1 to 20 carbon atoms, and wherein Z is selected from the group consisting of
- -
-
-
- Method for preparing bromofluorenes
-
A method for preparing bromofluorenes includes a step of dispersing a compound selected from the group consisting of fluorene, fluorenone, and derivatives of fluorene and fluorenone in water to prepare a disperse system. Bromination is initiated by adding bromine Br2 into the disperse system. Thus, bromofluorenes can be efficiently and economically prepared without using any environmentally harmful organic solvent requiring a high cost to dispose of.
- -
-
-
- Synthesis and liquid crystal phase behaviour of 2-(4-cyanophenyl)-7-n-alkylfluorenes: Luminescent mesogens
-
A new range of nematic liquid crystals containing the 2-phenylfluorene core has been prepared which may be considered as a model system for luminescent mesogens, which have potential interest as new display materials.
- Boardman, Frederick H.,Dunmur, David A.,Grossel, Martin C.,Luckhurst, Geoffrey R.
-
-
- The Synthesis of Bridged Oligophenylenes from Fluorene 1. Terphenyls and Quaterphenyls
-
Improved methods are presented for the alkylation of fluorene (2) to 9,9- dialkylfluorenes (3-6) free from 9-monoalkylfluorenes.Mono- and dihalogenated derivatives of 2-6 are reported as are a variety of ring substituted 9,9-dialkylfluorenes.Halogenated 9,9-dialkylfluorenes and aryl or methyl Grignard reagents were cross-coupled in Pd-catalyzed reactions to generate a series of novel p-oligophenylenes (four terphenyls (26, 27, 29 and 31c) and nineteen quterphenyls (33-6, 64-71 and 73-79)) each possessing one or two dialkylated methylene bridges between aromatic rings.Each bridged oligophneylene showed enhanced solubility, high quantum efficiency and photochemical stability.A number of quaterphenyls incorporated substituents which extended the conjugation of the oligophenylene chromophore.
- Kelley, Charles J.,Ghiorghis, Alem,Kauffman, Joel M.
-
p. 2701 - 2733
(2007/10/03)
-
- Halogenation Using N-Halogenocompounds. II. Acid Catalyzed Bromination of Aromatic Compounds with 1,3-Dibromo-5,5-dimethylhydantoin
-
Ring bromination of aromatic compounds using 1,3-dibromo-5,5-dimethylhydantoin in dichloromethane is promoted by the addition of strong acids.Both organic and inorganic acids whose pKa values are lower than -2 showed the promoting effect.This acid-catalyzed bromination is both practical and effective, even for aromatics having electron-withdrawing substituents.
- Eguchi, Hisao,Kawaguchi, Hideichiro,Yoshinaga, Sachiyo,Nishida, Akiko,Nishiguchi, Takeshi,Fujisaki, Shizuo
-
p. 1918 - 1921
(2007/10/02)
-
- Halogenation Using Quaternary Ammonium Polyhalides. XIV. Aromatic Bromination and Iodination of Arenes by Use of Benzyltrimethylammonium Polyhalides-Zinc Chloride System
-
The reaction of arenes with benzyltrimethylammonium tribromide or benzyltrimethylammonium dichloroiodate in acetic acid in the presence of ZnCl2 at room temperature or at 70 deg C gave brome- or iodo-substituted arenes in good yield, respectively.
- Kajigaeshi, Shoji,Kakinami, Takaaki,Moriwaki, Masayuki,Tanaka, Toshio,Fujisaki, Shizuo,Okamoto, Tsuyoshi
-
p. 439 - 443
(2007/10/02)
-
- The Decomposition of Arenediazonium Tetrafluoroborates with Halo- and Azidotrimethylsilanes in Nonaqueous Solvents
-
The reaction of arenediazonium tetrafluoroborates with chlorotrimethylsilane in a tetrahydrofuran/N,N-dimethylformamide (DMF) (5v/3v) solution afforded the protodediazotization products in high yields.The reactions of the diazonium salts with halotrimethylsilanes in DMF were found to give the corresponding haloarenes.Among the halodediazotization reactions, the iododediazotization with iodotrimethylsilane proceeded smoothly at room temperature to give the iodoarenes in excellent yields.In a similar manner, a variety of azidoarenes were obtained in cosistently high yields by the treatment of arenediazonium tetrafluoroborates with azidotrimethylsilane in a DMF solution.
- Keumi, Takashi,Umeda, Toshiaki,Inoue, Yoshinori,Kitajima, Hidehiko
-
-