- Phthalocyanine-cored fluorophores with fluorene-containing peripheral two-photon antennae as photosensitizers for singlet oxygen generation
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A series of free base and Zn(II) phthalocyanines featuring fluorenyl antennae linked by methoxy or oxo bridges to the phthalocyanine core (Pc) were synthesized and characterized. Selected linear and nonlinear (two-photon absorption) optical properties of these new compounds were subsequently studied. As previously observed for related porphyrin dendrimers bearing 2-fluorenyl peripheral dendrons, an efficient energy transfer occurs from the peripheral antennae to the central phthalocyanine core following excitation in the fluorenyl-based π–π* absorption band of these chromophores. Once excited, these compounds relax to the ground state, mostly by emitting intense red light or by undergoing intersystem crossing. As a result, the tetrafunctionalized Zn(II) phthalocyanines are fluorescent, but can also efficiently photosensitize molecular oxygen in tetrahydrofurane (THF), forming singlet oxygen with nearly comparable yields to bare Zn(II) phthalocyanine (ZnPc). In comparison with the latter complex, the positive role of the fluorenyl-containing antennae on one- and two-photon brightness (2PA) is presently demonstrated when appended in peripheral (β) position to the phthalocyanine core. Furthermore, when compared to known porphyrin analogues, the interest in replacing the porphyrin by a phthalocyanine as the central core to obtain more fluorescent two-photon oxygen photosensitizers is clearly established. As such, this contribution paves the way for the future development of innovative biphotonic photosensitizers usable in theranostics.
- Abid, Seifallah,Hassine, Sarra Ben,Richy, Nicolas,Camerel, Franck,Jamoussi, Bassem,Blanchard-Desce, Mireille,Mongin, Olivier,Paul, Frédéric,Paul-Roth, Christine O.
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Read Online
- New meso-Tetrafluorenylethynyl porphyrin platform
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To improve conjugation between a central porphyrin core and its peripheral fluorenyl antennae, we have introduced in the meso-Tetrafluorenyl porphyrin (TFP-Bu) unit an ethynyl spacer at the meso positions. By this means, we have synthesized and characterized a new meso-Alkynyl fluorenyl porphyrin (TAFlP). We discuss the effect of this extra extension of the I manifold on the optical properties. This enlarged porphyrin core, TAFlP, is foreseen as a key building block for the design of new dendrimers for theranostic applications. The constant improvement of porphyrin-based dendrimers featuring conjugated fluorenyl dendrons is recalled herein and demonstrates the important role of the central core structure in determining linear and nonlinear optical properties. Further improvement of these properties seems possible with TAFlP-like structures based on observations made for dendrimers recently obtained. This makes the exploration of such new molecular architectures appealing for photodynamic therapy (PDT) and related applications.
- Zhang, Xu,Paul-Roth, Christine O.
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Read Online
- Two-Photon Absorption and Cell Imaging of Fluorene-Functionalized Epicocconone Analogues
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Epicocconone 1 is a natural chromophore isolated from the fungus Epicoccum nigrum that has shown applications in proteomics and fluorescent microscopy thanks to its unique pro-fluorescence properties. The modification of the skeleton of the natural produc
- Oger, Samuel,Schapman, Damien,Mougeot, Romain,Leleu, Stéphane,Lascoux, No?lle,Baldeck, Patrice,Bénard, Magalie,Gallavardin, Thibault,Galas, Ludovic,Franck, Xavier
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Read Online
- Triindolo-Truxene Derivatives: Design, Synthesis, and Fine-Tuning of Electronic Properties and Molecular Assembly through Molecular Engineering
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Triindolo-truxene, a C3-symmetric molecule with a large π-conjugated plane, has six methylene carbon atoms and three aromatic carbon atoms that can be facilely functionalized. Herein, butyl, carbonyl, cyano, and/or malononitrile groups were int
- Chen, Jun-Bo,Zhou, Cen,Lu, Ru-Qiang,Wang, Xin-Chang,Qu, Hang,Saha, Mithu,Liu, Hao-Liang,Zhang, Hui,Cao, Xiao-Yu
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Read Online
- Novel hole transport material applied to solid-state dye-sensitized solar cell
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According to the design of the invention, a trifluorene ammonia compound is applied as a hole transport material to a solid-state dye-sensitized solar cell. Compared with common Spiro-OMeTAD, the compound has the characteristics that the molecular structure is simple, the solubility in an organic solvent is good, the compound and cations do not generate spectral competition with a photosensitizerand the like. The compound has a proper HOMO energy level and can be used as a hole transport material to be applied to a solid-state dye-sensitized solar cell.
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Paragraph 0036-0039
(2020/08/18)
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- Tacticity effects in side-chain photoluminescent polymers
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Stereoregular side-chain photoluminescent (PL) polymers were synthesized via the stereospecific polymerization of 9,9-dibutyl-2-(4-vinylphenyl)-9H-fluorene. The resulting isotactic, syndiotactic and atactic poly(9,9-dibutyl-2-(4-vinylphenyl)-9H-fluorene)
- Chiang, Cheng-Hung,Huang, Shih-Hung,Nien, Po-Chun,Chiang, Yeo-Wan,Tsai, Jing-Cherng
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supporting information
p. 13706 - 13709
(2019/01/03)
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- A study of two thermostable NLO chromophores with different π-electron bridges using fluorene as the donor
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Two chromophores C1 and C2 based on a fluorene electron donor with different π-electron bridges and the same electron acceptor have been synthesized and systematically characterized using NMR, MS and UV-vis absorption spectra. The energy gap between the ground state and the excited state and molecular nonlinearity were studied using UV-vis absorption spectroscopy, Density Functional Theory calculations and cyclic voltammetry measurements. The different properties between C1 and C2 were systematically compared. The results showed that C2 had a better performance than C1. The electrooptic coefficient of a poled film containing 25 wt% of C2 doped in amorphous polycarbonate afforded a value of 40 pm V-1 at 1310 nm. In addition, the excellent thermostability of C2 made itself a favourable candidate for practical application.
- Wang, Haoran,Liu, Fenggang,Yang, Yuhui,Zhang, Maolin,Peng, Chengcheng,Bo, Shuhui,Liu, Xinhou,Qiu, Ling,Zhen, Zhen
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p. 1038 - 1044
(2015/02/19)
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- Photoinitiators with fluorene structure and reactive liquid crystal compositions, and photoresist compositions comprising the same
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The present invention refers to fluorene novel photoinitiators and including reactive liquid crystal composition containing the polymer, and photosensitive composition, for forming a long wavelength UV curing an inner high absorptivity is excellent reactivity in which the, having excellent photo sensitivity reactive reaction prevention in and photosensitive composition liquid crystal composition having excellent compatibility fluorene novel photoinitiators and including reactive liquid crystal composition containing the polymer, and photosensitive composition is disclosed with a. [...] flue of the present invention to novel photoinitiators having represented by [general formula] is characterised in that it has a. [General formula] [General formula] in said R 1, R 2 each independently a hydrogen (the, R 1 and R 2 is is nothydrogen both.), for [formula 1] to [formula 9] in one from in groupit is indicatedstorehouse commencementit is selected, , R3, R 4 each independently a hydrogen, fluorine, carbon atoms is alkyl or branched hydridosiloxane and a linear in 1-6. (by machine translation)
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Paragraph 0201; 0204; 0205; 0217
(2016/12/01)
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- Fluorenylethynylpyrene derivatives with strong two-photon absorption: Influence of substituents on optical properties
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The one- and two-photon absorption properties of five newly synthesized pyrene-based chromophores with donor-π-acceptor, donor-π-acceptor-π-donor and acceptor-π-donor-π-acceptor structural motifs and with mono-, di- and tetra-branched fluorenyl groups linked to pyrene through an acetylene π-bridge are systematically studied both experimentally and theoretically. Analysis of the photophysical properties of the materials has been performed to derive structure-property relationships and to formulate guidelines for both spectral tuning and enhancement of molecular two-photon absorption cross-sections in the near-infrared spectral range. The influence of donor/acceptor strength, π-conjugation length, and molecular symmetry on the cross-sections of these new molecules has been studied. These dyes have high fluorescence quantum yields with good two-photon cross-sections ranging between 250 and 2500 GM. All of the tetra-substituted chromophores showed relatively strong two-photon absorption in the NIR region with cross-sections in the range of 1500-2500 GM at excitation wavelengths between 700 and 900 nm. Cross-sections as high as 9000 GM can be accessed at shorter wavelengths. The calculated two-photon absorption cross-section values and trends are in good agreement with the experimental results. It was found that the presence of donor or acceptor groups increases the 2PA cross-sections relative to molecules with simple aryl substituents. Increasing the donor strength is conducive to attain large two-photon cross-sections. Moreover, the combination of large two-photon absorption cross-sections and high fluorescence quantum yields makes these dyes good two-photon chromophores for a variety of applications.
- Lavanya Devi,Yesudas,Makarov, Nikolay S.,Jayathirtha Rao,Bhanuprakash,Perry, Joseph W.
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p. 3730 - 3744
(2015/04/22)
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- New bithiazole-functionalized organic photosensitizers for dye-sensitized solar cells
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Five bithiazole-based organic dyes D1-D5 containing different electron donor moieties (thiophene, uorene, carbazole, and triarylamine) in the molecular frameworks were synthesized, characterized and applied in dye-sensitized solar cells (DSSCs). The effects of electron-donating moieties of the organic dyes on their photophysical, electrochemical, and photovoltaic properties have been investigated in detail. These dyes exhibit strong charge transfer absorption bands in the visible region. Their redox potential levels were estimated by cyclic voltammetry and found to match well with the charge flow in DSSCs. The combination of broad absorption bands with fairly high extinction coefficients and appropriate redox properties makes these bithiazole-based molecules promising dyes for DSSCs. For solar cell device based on D4, the maximal monochromatic incident photon-to-current conversion efficiency (IPCE) can reach up to 68.5%, with a short-circuit photocurrent density (Jsc) of 9.61 mA cm-2, an open-circuit photovoltage (Voc) of 0.70 V and a fill factor (FF) of 0.70, which results in a power conversion efficiency (PCE) of 4.65% under illumination of an AM 1.5 solar cell simulator.
- Lai, Lai-Fan,Ho, Cheuk-Lam,Chen, Yung-Chung,Wu, Wen-Jun,Dai, Feng-Rong,Chui, Chung-Hin,Huang, Shu-Ping,Guo, Kun-Peng,Lin, Jiann-T'Suen,Tian, He,Yang, Shi-He,Wong, Wai-Yeung
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p. 516 - 524
(2013/02/22)
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- The synthesis, photophysical and electrochemical properties of a series of novel 3,8,13-substituted triindole derivatives
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The synthesis and properties of a series of new 3,8,13-substituted triindole derivatives 1a-1e are reported. The 3,8,13-substituted triindoles were thermally robust with high decomposition temperatures (≥405°C) and high melt transitions (219°C-373°C). Compound 5e was crystallized in the monoclinic system with the space group P21/n. These compounds showed UV-Vis absorption (λmaxAbs) in the range of 311-345 nm in DCM solution and 371-391 nm in solid state, and fluorescence maxima (λmaxEm) in the range of 394-412 nm in DCM solution and 416-461 nm in solid state. The fluorescence quantum yields ranged from 0.27 to 0.58. The estimated electron affinities (LUMO levels) and estimated ionization potential (HOMO levels) of compounds 1a-1e are 3.54-3.71 eV and 5.12-5.48 eV, respectively. Quantum chemical calculations using DFT B3LYP/6-31G showed nearly identical LUMO (-0.72 to -1.10 eV) and HOMO (-4.65 to -4.84 eV) values. These results demonstrated that the new 3,8,13-substituted triindoles are promising thermally stable host materials for organic light-emitting diodes with reasonable hole mobility.
- Zhu, Tianhao,He, Guangke,Chang, Jin,Zhao, Dongdong,Zhu, Xiaolin,Zhu, Hongjun
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p. 679 - 688
(2012/11/07)
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- Blue-light-emitting multifunctional triphenylamine-centered starburst quinolines: Synthesis, electrochemical and photophysical properties
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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
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scheme or table
p. 4704 - 4711
(2012/08/08)
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- Novel multifunctional organic semiconductor materials based on 4,8-substituted 1,5-naphthyridine: Synthesis, single crystal structures, opto-electrical properties and quantum chemistry calculation
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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
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scheme or table
p. 6693 - 6704
(2012/09/22)
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- Generation and spectroscopic profiles of stable multiarylaminium radical cations bridged by fluorenes
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A series of arylaminofluorene derivatives (DTFA-1, TTFA-2, TAFB-3, and TAFA-4) were synthesized, and the generation of their corresponding arylaminium cation radicals was readily achieved by Cu(ClO4)2 in CH3CN. Moreover, t
- Chang, Chao-Che,Yueh, Han,Chen, Chao-Tsen
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supporting information; experimental part
p. 2702 - 2705
(2011/06/26)
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- Synthesis and structureproperty relationships of symmetric ambipolar quaterfluorene-containing oxadiazole as a central core and diphenylamine as end-capping moieties
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A facile approach for the synthesis of the symmetric ambipolar quaterfluorene, OF(4)OX-NPh, with hole-transporting and electron-transporting moieties by Suzuki cross-coupling as a key reaction has been developed. This novel ambipolar quaterfluorene exhibi
- Yang, Fan,Zhang, Xiao Ling,Xiong, Mo Jun,Cao, Zi Jian,Xia, Ping Fang,Li, Zhong Hui
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p. 541 - 546
(2008/12/20)
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- Electron transport agents for organic electronic devices
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Compounds and compositions are provided that can be used as electron transport agents in organic electronic devices such as organic electroluminescent devices. The compounds are non-polymeric and have an aromatic core conjugated to end capping groups. The aromatic core contains a phenylene group arylene or naphthalene group arylene having a pendant heteroaryl group that includes a —C═N— unit.
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- Diphenylamino end-capped oligofluorenes with enhanced functional properties for blue light emission: Synthesis and structure-property relationships
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A novel series of monodisperse asymmetrically and symmetrically substituted diphenylamino end-capped oligofluorenes, OF(2)-NPhR, R = H or An (An = 9-anthryl) and OF(n)-NPh, n = 2-4, has been synthesized by a convergent approach using palladium-catalyzed S
- Li, Zhong Hui,Wong, Man Shing,Tao, Ye,Lu, Jianping
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p. 3285 - 3293
(2007/10/03)
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- REACTIVITY OF CARBANIONS. XIV. KINETICS OF THE ALKYLATION OF CARBANIONS OF THE FLUORENYL TYPE AND THEIR ION PAIRS BY BUTYL BROMIDE
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The reaction rate constants were determined for the free carbanions and their ion pairs in the reaction of the lithium and cesium salts of 9-cyano-, 9-methoxycarbonyl-, 9-phenyl-, 9-triphenylmethyl-, 9-trimethylsilyl-, 9-benzyl-, 9-methyl-, 9-tert-butyl-, 2-cyano-, 2-bromo-, 2-methyl-, and 2-dimethylaminofluorenes, fluorene, 1-azafluorene, 3-methyl-2-azafluorene, 1,2-benzofluorene, and fluoradene with butyl bromide in dimethoxyethane at 25 gradC.The obtained data can be used as the basis for the creation of a scale of relative nucleophilicity in the carbanions.
- Solov'yanov, A. A.,Beletskaya, I. P.,Reutov, O. A.
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p. 1592 - 1603
(2007/10/02)
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