- Synthesis, characterization, and optical properties of 2-amino-4-aryl-6-(9, 9′-spirobifluoren-2-yl)pyrimidines
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A series of 2-amino-4-aryl-6-(9,9′-spirobifluoren-2-yl)pyrimidines have been synthesized by the reaction of guanidine and chalcones under basic conditions. The physical and optical properties indicated that these compounds generally show good blue light e
- Shi, Yingbo,Liu, Qiancai,Tang, Jie
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- HETEROATOMIC-BASED HOLE-TRANSPORT MATERIALS
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Heteroatomic hole transport materials are provided. The hole transport materials include a non-carbon core: two, four, or eight aromatic groups covalently bound to the non-carbon core; a. terminal substituted diphenylamine end unit on each aromatic group: and optionally aromatic linker groups linking the aromatic groups and the substituted diphenylamine end units. In some embodiments the non-carbon core is non-carbon central atom such as Si, Ge, B?, P+Sn or Pb. In other embodiments, the non-carbon core is a cubic silsesquioxane. Also provided are methods for making these materials. The materials are particularly useful as hole transport materials in perovskite solar cells.
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Paragraph 0013
(2021/04/30)
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- Synthesis of Conjugated Copolymer Containing Spirobifluorene Skeleton by Acyclic Diene Metathesis Polymerization for Polymer Light-Emitting Diode Applications
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Grubbs-type, Hoveyda-type, cyclic alkyl amino carbene (CAAC)-based ruthenium olefin metathesis catalysts were used for the acyclic diene metathesis (ADMET) polymerization of 2,7-divinyl-9,9-di-n-octylfluorene (DVF). Additionally, various ratios of DVF and 2,2′,7,7′-tetravinyl-9,9′-spirobifluorene (TVSF) were subjected to ADMET polymerization to obtain polymers P1–P7. Polymers P1–P4 were analyzed with gel permeation chromatography, UV–vis spectroscopy, and photoluminescence spectroscopy. As the TVSF ratio increases, polymers exhibit lower solubility but a narrower band in the photoluminescence spectrum. Polymer light-emitting diode (PLED) devices were fabricated with polymers P1, P2, and P3. The performances of the PLED devices indicated that polymers including more spirobifluorene blocks showed better turn-on voltage, brightness, current efficiency, and power efficiency.
- Park, Seongwook,Jeong, Soyeong,Kang, Changmuk,Hong, Sukwon
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supporting information
p. 929 - 933
(2021/05/07)
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- Method for synthesizing 9,9'-spirobifluorene derivative
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The invention relates to a method for synthesizing a 9,9'-spirobifluorene derivative, and belongs to the field of organic chemical synthesis. The method comprises the following steps: activating a C-Fbond in tetrahydrofuran under inert gas protection through reduction and lithiation reaction of raw materials of 2-fluorobiphenyl and a metal lithium sheet, thus establishing 2-biphenyl lithium; thenenabling the 2-biphenyl lithium to react with a fluorenone derivative, hydrolyzing, drying a solvent by distillation, and carrying out ring closing on solid in acetic acid, thus synthesizing the 9,9'-spirobifluorene derivative. According to the method disclosed by the invention, the 2-fluorobiphenyl in low cost is adopted as a raw material to replace 2-bromobiphenyl commonly adopted by a traditional method, the production cost is low, and reaction conditions are gentle; an applicable substrate range of the method is wide, and a new thought is provided for synthesis of the 9,9'-spirobifluorenederivative.
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Paragraph 0033; 0034
(2019/01/05)
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- 9, 9' - Spirobifluorene preparation of
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PROBLEM TO BE SOLVED: To provide a method for industrially advantageously manufacturing 9,9'-spirobifluorenes.SOLUTION: By performing a reaction in the presence of a non-aqueous solvent when an intermediate (9-(2-biphenyl)-9-fluorene alcohols) is ring-closed, 9,9'-spirobifluorenes are obtained even when a large amount of acid is not used as a solvent. In the manufacture of the intermediate, the 9,9'-spirobifluorenes can be more easily manufactured by extracting the intermediate 9-(2-biphenyl)-9-fluorene alcohols obtained by a Grignard reaction between 2-halo biphenyl and 9-fluorenones from a reaction mixture by a water-insoluble solvent instead of a method of isolating the intermediate by a crystallization filtration being a conventional method.
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Paragraph 0047
(2018/04/20)
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- Bigger and Brighter Fluorenes: Facile π-Expansion, Brilliant Emission and Sensing of Nitroaromatics
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π-Expanded butterfly-like 2D fluorenes and 3D spirobifluorenes 1–5 were synthesized via a DDQ-mediated oxidative cyclization strategy with a high regioselectivity. Through structural modification via π-expansion, it was possible to achieve near-ultraviolet absorption, bright-blue emission, very high near-unity fluorescence quantum yields in solution as well as in film states, and deep-lying HOMO energy levels with excellent thermal stabilities. Furthermore, these electron-rich compounds displayed a notable behavior towards sensing of nitroaromatic explosives, such as picric acid, up to a detection limit of 0.2 ppb.
- Ramakrishna, Jagarapu,Venkatakrishnan, Parthasarathy
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supporting information
p. 181 - 189
(2017/02/05)
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- Facile synthesis of a hole transporting material with a silafluorene core for efficient mesoscopic CH3NH3PbI3 perovskite solar cells
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A novel electron-rich small-molecule, 4,4′-(5,5-dihexyl-5H-dibenzo[b,d]silole-3,7-diyl)bis(N,N-bis(4-methoxyphenyl)aniline) (S101), containing silafluorene as the core with arylamine side groups, has been synthesized via a short efficient route. When S101 was incorporated into a CH3NH3PbI3 perovskite solar cell as a hole transporting material (HTM), a short circuit photocurrent density (Jsc) of 18.9 mA cm-2, an open circuit voltage (Voc) of 0.92 V, and a fill factor (FF) of 0.65 contributing to an overall power conversion efficiency (PCE) of ~11% which is comparable to the PCE obtained using the current state-of-the-art HTM 2,2′,7,7′-tetrakis(N,N′-di-p-methoxyphenylamine)-9,9′-spirobifluorene (spiro-OMeTAD) (η = 12.3%) were obtained. S101 is thus a promising HTM with the potential to replace the expensive spiro-OMeTAD due to its comparable performance and much simpler and less expensive synthesis route.
- Krishna, Anurag,Sabba, Dharani,Yin, Jun,Bruno, Annalisa,Antila, Liisa J.,Soci, Cesare,Mhaisalkar, Subodh,Grimsdale, Andrew C.
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p. 8750 - 8754
(2016/06/14)
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- Novel compounds for organic electroluminescent device
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Provided is a compound which is represented by chemical formula 1, and is used to manufacture an organic electroluminescent device. According to the present invention, the compound has high hole mobility, high thermal stability, a high band gap energy, a
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Paragraph 0074; 0076; 0077-0079
(2017/07/23)
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- Self-assembly of metallosupramolecular rhombi from chiral concave 9,9'-spirobifluorene-derived bis(pyridine) ligands
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Two new 9,9'-spirobifluorene-based bis(4-pyridines) were synthesised in enantiopure and one also in racemic form. These ligands act as concave templates and form metallosupramolecular [(dppp)2M2L2] rhombi with cis-protected [(dppp)Pd]2+ and [(dppp)Pt]2+ ions. The self-assembly process of the racemic ligand preferably occurs in a narcissistic self-recognising manner. Hence, a mixture of all three possible stereoisomers [(dppp)2M2{(R)-L}2](OTf)4, [(dppp)2M2{(S)-L}2](OTf)4, and [(dppp)2M2{(R)-L}{(S)- L}](OTf)4 was obtained in an approximate 1.5:1.5:1 ratio which corresponds to an amplification of the homochiral assemblies by a factor of approximately three as evidenced by NMR spectroscopy and mass spectrometry. The racemic homochiral assemblies could also be characterised by single crystal X-ray diffraction.
- Hovorka, Rainer,Hytteballe, Sophie,Piehler, Torsten,Meyer-Eppler, Georg,Topic, Filip,Rissanen, Kari,Engeser, Marianne,Luetzen, Arne
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p. 432 - 441
(2014/03/21)
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- Highly efficient synthesis of polysubstituted fluorene via iron-catalyzed intramolecular Friedel-Crafts alkylation of biaryl alcohols
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An efficient and mild Fe(III)-catalyzed intramolecular Friedel-Crafts alkylation of biaryl methanol derivatives has been developed to achieve the substituted fluorene derivatives. The present reaction provides an excellent alternative to published methods
- Sarkar, Soumen,Maiti, Sukhendu,Bera, Krishnendu,Jalal, Swapnadeep,Jana, Umasish
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p. 5544 - 5547
(2012/11/07)
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- A joint experimental and theoretical investigation on nonlinear optical (NLO) properties of a new class of push-pull spirobifluorene compounds
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A new class of push-pull spirobifluorene compounds 1-5 has been synthesized. The nonlinear optical (NLO) properties (first and second hyperpolarizability β and γ, respectively) of spirobifluorene derivatives have been investigated for the first time using electric field induced second harmonic (EFISH) and third harmonic generation (THG) methods. Moreover, a comparison with the corresponding push-pull fluorene monomers 1a-5a was carried out. Besides the experimental data, ab initio theoretical calculations on structural, electronic, and optical properties were carried out for all compounds. The analyses indicate that an increase in the β and γ values occur on passing from monomers to dimers without compromising the optical transparency.
- Rizzo, Fabio,Cavazzini, Marco,Righetto, Stefania,De Angelis, Filippo,Fantacci, Simona,Quici, Silvio
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scheme or table
p. 4004 - 4016
(2010/09/18)
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- Synthesis of diaza-analogue of fluorenone and spirobifluorene
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The effective syntheses of diaza-analogue of fluorenone and spirobifluorene with N=N bond has been conducted with the using of ninhydrin and corresponding acetyl derivatives of arenes. Single-crystal X-ray diffraction of 2-(spirobifluoren-2-yl)-3,4-dizasp
- Wu, Guo-Hong,Liu, Qian-Cai,Tang, Jie
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scheme or table
p. 1157 - 1168
(2011/03/22)
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- Simple and efficient method for obtaining fluorene and spirobifluorene bromide derivatives
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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
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p. 1888 - 1895
(2008/09/20)
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- Head-to-tail regioregular oligothiophene-functionalized 9,9′-spirobifluorene derivatives. 1. Synthesis
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Two series of novel fully conjugated oligomers, oligothiophene-functionalized 9,9′-spirobifluorene derivatives, have been developed in this contribution. First, four 9,9′-spirobifluorene bromide derivatives (compounds 1a-d) are prepared through various synthetic routes. Oligothiophene derivatives with or without substituents are synthesized through the Grignard and Suzuki coupling reactions. The Negishi coupling reactions between oligothienylzinc chloride and various 9,9′spirobifluorene bromides with Pd(PPh3)4 as catalyst successfully produce the desired compounds, unsubstituted oligothiophene-functionalized 9,9′-spirobifluorene derivatives, compounds 2 to 4ad. Since the Negishi coupling reactions afford regioregularly head-to-tail (H-T) oligo(4-nhexylthiophene)-functionalized 9,9′-spirobifluorene derivatives in poor yields, the Suzuki coupling reactions between sodium 4-n-hexylthienyl-2-boronate 8, and various 9,9′-spirobifluorene-based bromides 1a-d and 9-16 are employed to produce highly regioregular head-to-tail oligothiophenefunctionalized 9,9′-spirobifluorene derivatives (compounds 5 to 7a-d) in very high yields. We also investigate the effect of solvents on the Suzuki coupling reactions. The structure and purity of all compounds are verified by FT-IR, 1H and 13C NMR, MS, and elemental analysis.
- Pei, Jian,Ni, Jing,Zhou, Xing-Hua,Cao, Xiao-Yu,Lai, Yee-Hing
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p. 4924 - 4936
(2007/10/03)
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- Convergent synthetic routes to orthogonally fused conjugated oligomers directed toward molecular scale electronic device applications
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This paper describes the synthetic organic phase of a project directed toward the construction of molecular scale electronic devices. Outlined is a convergent synthetic route to orthogonally fused conjugated organic oligomers. The final systems are to have a potentially conducting chain fused perpendicularly to a second potentially conducting chain via a a bonded network. One of the core segments synthesized is based on a spirobithiophene moiety with a central silicon atom. It is formed by a zirconium-promoted bis(bicyclization) of a tetrapropargylsilane. The second core is a 9,9′-spirobifluorene system. Terminal halide groups provide the linkage points for further extension of the chains via Pd-catalyzed or Pd/Cu-catalyzed cross coupling methods. All four branching arms are affixed to the core in a single operation, thus making the syntheses highly convergent. In the cases of the larger functionalized systems, alkyl substituents on the thiophenes afford soluble materials. In order to prepare the molecules with > 50 A lengths, an iterative divergent/convergent approach had to be utilized for the construction of oligo(thiophene-ethynylene) branching arms. Organopalladium-catalyzed procedures are used extensively for the syntheses of the orthogonally fused compounds.
- Wu, Ruilian,Schumm, Jeffry S.,Pearson, Darren L.,Tour, James M.
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p. 6906 - 6921
(2007/10/03)
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- Versatile and Convenient Lattice Hosts derived from Singly Bridged Triarylmethane Frameworks, X-Ray Crystal Structures of Three Inclusion Compounds
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A new family of host molecules, based on the singly bridged triarylmethanol and triarylacetic acid frameworks, is described.These hosts form crystalline inclusions with a variety of uncharged organic molecules ranging from protic dipolar to apolar compounds (130 different species).The formation and stoicheiometry depend in a systematic manner on structural parameters of the host, such as the nature of the functional group and the substituents, and on the substituent positions.The crystal structures of three inclusion compounds have been studied by X-ray diffraction.They reveal the building principles of the new inclusion family.In the crystals of 1a*benzene (8:3), the benzene is interstitially entrapped by H-bonded tetramer clusters of 1a.Crystals of 1a*dioxane (4:3) are built of H-bonded 2:1 host-guest complexes including interstitial molecules of dioxane.In the case of 4c*EtOH (1:1), the building principle is formation of 2:2 host-guest clusters via a twelve-membered H-bonded ring.
- Weber, Edwin,Doerpinghaus, Norbert,Csoeregh, Ingeborg
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p. 2167 - 2177
(2007/10/02)
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