- Toward stable interfaces in conjugated polymers: Microporous poly(p-phenylene) and poly(phenyleneethynylene) based on a spirobifluorene building block
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Conjugated polymer networks based on spirobifluorene building units exhibit defined photoluminescence as well as pronounced microporosity, that is, large, stable interfaces. Copyright
- Weber, Jens,Thomas, Arne
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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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- 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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- Nonlinear-Optical Behaviors of a Chiral Metal-Organic Framework Comprised of an Unusual Multioriented Double-Helix Structure
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We present here the synthesis of one enantiomeric pair of metal-organic framework materials comprised of a unique multioriented double-helix structure from an achiral spirocenter ligand. Our study clearly shows that the chiral MOF material encompasses concurrently multiple nonlinear-optical functions in the solid state: the noncentrosymmetric structural feature brings the chiral MOF high second-harmonic-generation efficiency; the incorporation of the spirocenter ligand can efficiently produce two-photon-excited photoluminescence with a larger-action cross-sectional value.
- Huang, Xiaoli,Li, Qiyang,Xiao, Xue,Jia, Shuping,Li, Yue,Duan, Zhigang,Bai, Lei,Yuan, Ze,Li, Lin,Lin, Zhihua,Zhao, Yonggang
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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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- 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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- Triptycenyl Sulfide: A Practical and Active Catalyst for Electrophilic Aromatic Halogenation Using N-Halosuccinimides
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A Lewis base catalyst Trip-SMe (Trip = triptycenyl) for electrophilic aromatic halogenation using N-halosuccinimides (NXS) is introduced. In the presence of an appropriate activator (as a noncoordinating-anion source), a series of unactivated aromatic compounds were halogenated at ambient temperature using NXS. This catalytic system was applicable to transformations that are currently unachievable except for the use of Br2 or Cl2: e.g., multihalogenation of naphthalene, regioselective bromination of BINOL, etc. Controlled experiments revealed that the triptycenyl substituent exerts a crucial role for the catalytic activity, and kinetic experiments implied the occurrence of a sulfonium salt [Trip-S(Me)Br][SbF6] as an active species. Compared to simple dialkyl sulfides, Trip-SMe exhibited a significant charge-separated ion pair character within the halonium complex whose structural information was obtained by the single-crystal X-ray analysis. A preliminary computational study disclosed that the πsystem of the triptycenyl functionality is a key motif to consolidate the enhancement of electrophilicity.
- Nishii, Yuji,Ikeda, Mitsuhiro,Hayashi, Yoshihiro,Kawauchi, Susumu,Miura, Masahiro
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supporting information
p. 1621 - 1629
(2020/02/04)
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- {[Ru(bda)]:XLy}n cross-linked coordination polymers: Toward efficient heterogeneous catalysis for water oxidation in an organic solvent-free system
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Recently, the development of polymeric catalysts for water splitting has received an increasing amount of attention. In this study, we successfully developed a few novel cross-linked coordination polymers (CCPs) with the formula {[Ru(bda)]xLy}n as efficient heterogeneous catalysts for water oxidation in an organic solvent-free system, where Ru(bda) represents the catalytic center. Detailed water oxidation catalytic kinetics studies suggested that single-site water nucleophilic attack (WNA) is the general mechanism applied to these polymeric catalysts, which is different to the small-molecular reference, [Ru(bda)(pic)2] (pic = 4-picoline). The experimental evidence also indicated the importance of interfacial wettability and the existence of the Ru(bda)-macrocyclic fragments in the polymer network in determining the overall catalytic activity. More interestingly, end-capping modification via the pyridine/DMSO exchange reaction further removed the residual Ru(DMSO)x moieties on the surfaces of the polymer network, which leads to the improved performance with an impressive TOF of ～4.6 s-1 and TON of ～750 in an organic solvent-free system, which are superior to [Ru(bda)(pic)2]. The rate of catalysis is among the highest for a heterogeneous system reported to date. An electrochemical study showed the polymeric catalysts were also promising electrode materials for electrocatalytic water oxidation and an electrode based on CCP/Nafion/ITO maintained ～73% of its initial activity after 27 cycles under the optimal conditions.
- Zheng, Tao,Li, Lianwei
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supporting information
p. 2526 - 2536
(2018/02/19)
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- Spirofluorene compound and light-emitting device thereof
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The invention relates to the technical field of organic light-emitting materials and particularly relates to a spirofluorene compound and a light-emitting device thereof. A spirobifluorene compound is selected from a compound represented by formula I (shown in the description), wherein Y1 and Y2 respectively independently represent hydrogen, electron-withdrawing groups or electron-donating groups; at least one of X1 and X2 represents a substituent represented by formula II (shown in the description); M represents -S-, -P-, -SO-, -SO2-, -S(=S)-, -S(=S)(=S)-, -PO-, -PO2-, -P(=S)-, -P(=S)(=S)- and -C(=O)-; N1, N2, N3 and N4 respectively independently represent carbon atoms or nitrogen atoms; and n represents an integer of 0-4. The spirobifluorene compound disclosed by the invention has an A-D-A chemical structure, and a spatial dihedral angle close to 90 degrees is formed between an electron-donating D unit and an electron-withdrawing A unit, so that HOMO-LUMO track separation of a fluorescent material is beneficially thermally activated and delayed, so as to obtain ideal deltaEST.
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Paragraph 0125; 0126; 0127
(2017/09/01)
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- Fluorinated 9,9′-spirobifluorene derivatives as host materials for highly efficient blue organic light-emitting devices
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A series of new fluorinated 9,9′-spirobifluorene derivatives (SFs) have been designed and synthesized for organic light-emitting devices (OLEDs). The spatial structure of 2,2′,7,7′-tetrakis(2,4-bifluorophenyl) spiro-9,9′-bifluorene was determined by X-ray diffraction analysis. With the different substitution patterns of electron-withdrawing groups, such as F and CF3, the photophysical properties, energy levels and thermal stabilities of these SFs can be tuned, which is supported by density functional studies of their geometries and electronic structures. A non-doped deep blue OLED using 2,2′,7,7′-tetrakis(3-fluorophenyl)spiro-9,9′- bifluorene (Spiro-(3)-F) as the emitter shows excellent Commission Internationale de l'Eclairage (CIE) coordinates of (0.169, 0.122) with emission peaking at ca. 408 nm. Furthermore, these SFs serve as an excellent host material for the 4,4′-bis(9-ethyl-3-carbazovinylene)-1,1′- biphenyl dopant to form high-performance OLEDs with low turn-on voltages and high efficiencies, especially for Spiro-(3)-F as the fluorescent host with pure blue CIE coordinates of (0.149, 0.187), a low turn-on voltage of 3.4 V, high luminance of over 10 000 cd m-2, a high current efficiency of 6.66 cd A-1, and a high external quantum efficiency of 4.92%. The high efficiency is attributed to the high carrier mobility together with the low injection barriers for both the electron and the hole in the Spiro-(3)-F-based device.
- Li, Zhanfeng,Jiao, Bo,Wu, Zhaoxin,Liu, Peng,Ma, Lin,Lei, Xiaoli,Wang, Dongdong,Zhou, Guijiang,Hu, Huaiming,Hou, Xun
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p. 2183 - 2192
(2013/05/23)
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- Liquid triarylamines: The scope and limitations of piers-rubinsztajn conditions for obtaining triarylamine-siloxane hybrid materials
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New liquid triarylamine-siloxane hybrid materials are produced using the Piers-Rubinsztajn reaction. Under mild conditions, liquid analogues of conventional and commonly crystalline triarylamines are easily synthesized from readily available or accessible intermediates. Using a diverse selection of triarylamines, we explored the effects of siloxane group and substitution pattern on the physical properties of these materials, and we have demonstrated that relatively large molecular liquids with desirable electrochemical properties can be produced. The interactions between the strongly Lewis acidic catalyst used for this transformation, tris(pentafluorophenyl)borane (BCF), and the Lewis basic triarylamine substrates were studied. Through UV-vis-NIR and 19F NMR spectroscopy, we have proposed that the catalyst undergoes a reversible redox reaction with the substrates to produce a charge transfer complex. The formation of this charge transfer complex is sensitive to the oxidation potential of the triarylamine and can greatly affect the kinetics of the Piers-Rubinsztajn reaction.
- Kamino, Brett A.,Mills, Bridget,Reali, Christopher,Gretton, Michael J.,Brook, Michael A.,Bender, Timothy P.
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experimental part
p. 1663 - 1674
(2012/04/17)
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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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- Novel hole transporting material and solid electrolyte to be applied in a photovoltaic device
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Disclosed herein is a material, and a solid electrolyte and a photovoltaic device using the same. When the material is used as a hole transporting layer material of the photovoltaic device, the reduction of an electrolytic layer resulting from leakage or volatilization of an electrolytic solution is prevented, thus the battery characteristics, long-term stability, and reliability of the photovoltaic device are improved.
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Page/Page column 6-7
(2008/06/13)
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- Spiro compounds and their use
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Spiro compounds of the formula (I), in which at least one of the radicals K1, L, M, N1, R1, R2, R3, R4 is one of the following groups are suitable as charge transport materials, in particular for photovoltaic cells, and as electroluminescence materials.
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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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- USE OF SPIRO COMPOUNDS AS LASER DYES
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Use of spiro compounds of formula (I), where K and K are, independently of one another, conjugated systems, as a laser dye.
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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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- Compound for use in the synthesis of semiconducting polymers with perpendicularly arranged cores and method of synthesizing said compound
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The stereochemical structure necessary for preparation of perpendicularly arranged cores is provided by a compound of the formula STR1 This compound can be synthesized by the reaction of STR2 with bromine in the presence of FeCl3.
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