- Synthesis of new bis-BINOLs linked by a 2,2e′-bipyridine bridge
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A series of new C2-symmetric chiral ligands 8, 9, 11 and 12, consisting of two binaphthyl units linked by a 2,2′-bipyridine bridge, has been synthesized via Suzuki cross-coupling reactions.
- Bai, Xiao-Li,Liu, Xu-Dong,Wang, Mang,Kang, Chuan-Qing,Gao, Lian-Xun
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- Photoinduced Electron Transfer Coupled to Donor Deprotonation and Acceptor Protonation in a Molecular Triad Mimicking Photosystem II
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The first artificial donor-sensitizer-acceptor compound in which photoinduced long-range electron transfer is coupled to donor deprotonation and acceptor protonation is reported. The long-lived photoproduct stores energy in the form of a radical pair state in which the charges of the donor and the acceptor remain unchanged, much in contrast to previously investigated systems that exhibit charge-separated states comprised of electron-hole pairs. This finding is relevant for light-driven accumulation of redox equivalents, because it exemplifies how the buildup of charge can be avoided yet light energy can be stored. Proton-coupled electron transfer (PCET) reactions at a phenol donor and a monoquat acceptor triggered by excitation of a Ru(II) sensitizer enable this form of photochemical energy storage. Our triad emulates photosystem II more closely than previously investigated systems, because tyrosine Z is oxidized and deprotonated, whereas plastoquinone B is reduced and protonated.
- Pannwitz, Andrea,Wenger, Oliver S.
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- A straightforward synthesis of 5-bromo and 5,5'-dibromo-2,2'-bipyridines
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We herein report on the selective synthesis of 5-bromo-2,2'-bipyridine 2 and 5,5'-dibromo-2,2'-bipyridine 3 by direct bromination of 2,2'-bipyridine hydrobromide salt 1, as well as by radical decarboxylative bromination of the corresponding acid chlorides.
- Romero,Ziessel
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- A Bipyridine-Based Conjugated Microporous Polymer for the Ir-Catalyzed Dehydrogenation of Formic Acid
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Formic acid is considered a promising energy storage medium, and its selective dehydrogenation enables the generation of high-purity H2. Herein we report a bipyridine-based conjugated microporous polymer (CMP) loaded with [Cp?IrCl2]2 for the base-free aqueous dehydrogenation of formic acid to H2/CO2. This catalyst exhibits high activity and selectivity at temperatures over 130 °C and with formic acid concentrations as high as 10 M. Recycling tests demonstrate a low Ir leaching and a gradual increase in the activity over six runs and a low CO content in the gas phase of about 138 ppm. TOFs of up to 123894 h-1 were obtained using 0.1 wt % Ir loading.
- Broicher, Cornelia,Foit, Severin R.,Rose, Marcus,Hausoul, Peter J.C.,Palkovits, Regina
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- Cyclometalated iridium(III) complexes as photosensitizers for long-range electron transfer: Occurrence of a coulomb barrier
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Six cyclometalated iridium(III) complexes were investigated to assess their potential as photosensitizers for long-range electron transfer, and two of them were incorporated directly into covalent donor-bridge-acceptor molecules. The influence of ligarid substitutions on the excited-state properties and the photoredox behavior of the iridium complexes was explored by optical absorption, steady-state and time-resolved luminescence spectroscopy, as well as by electrochemical methods. Bimolecular electron transfer between the photoexcited complexes and 10-methylphenothiazine and methylviologen was found to be only weakly dependent on the ligand substitutions. Intramolecular long-range electron transfer from phenothiazine to photoexcited iridium(III) in the dyads is slow due to the occurrence of a Coulomb barrier. Consequently, an electron-transfer photoproduct is only observable in the transient absorption spectrum, of a donorbridge-acceptor molecule with a fluorinated photosensitizer that exhibits a very long excited-state lifetime. A flashquench technique is necessary for detection of an electrontransfer product in the dyad with a non-fluorinated photosensitizer. The occurrence of a Coulomb barrier associated with intramolecular (excited-state) long-range electron transfer in the dyads with cyclometalated iridium(III) photosensitizers represents an important difference to previously investigated similar donor-bridge-acceptor molecules with photosensitizers based on d6 metal diimine complexes.
- Hanss, David,Freys, Jonathan C.,Bernardinelli, Gerald,Wenger, Oliver S.
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- Bromination of 2,2'-bipyridile
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A simple and convenient procedure was developed for the synthesis of 5,5'-dibromo-2,2'-bipyridyl providing the target compound in a high yield without the chromatographic separation of the reaction mixture. Polybromo derivatives of 2,2'-bipyridyl were isolated and characterized for the first time. Nauka/Interperiodica 2006.
- Zdravkov,Khimich
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- Development of high dielectric polyimides containing bipyridine units for polymer film capacitor
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Polymer dielectrics with high dielectric constant, low dielectric loss, high breakdown strength, and high temperature capability are attractive for applications such as capacitive energy-storage. Commercially available polymer dielectrics such as biaxially oriented polypropylene (BOPP), poly(ethylene terephthalate) (PET), poly(ethylene naphthalate) (PEN), polycarbonate (PC), and poly(vinylidene) fluoride (PVDF) can be just operated below 200 °C. Great effort has been put into exploring high temperature polymer dielectrics to fulfill the demand of high temperature applications, such as the aerospace and military power supply. In this study, a series of polyimides containing bipyridine units with good dielectric performance and high temperature capability were prepared by using a newly synthesized diamine monomer, (5,5′-bis [(4-amino) phenoxy]-2,2′-bipyridine (BPBPA)). These polyimides possessed high dielectric constant of the as-synthesized polyimides can be up to7.2, the dielectric loss was 3. Furthermore, the polyimides exhibited high glass transition temperature (Tg) of 275–320 °C and tensile strengths of 175–221 MPa. These obtained polyimides promise potential applications in high temperature flexible polymer film capacitor operated at high temperature.
- Peng, Xinwen,Xu, Wenhui,Chen, Linlin,Ding, Yichun,Xiong, Tianrou,Chen, Shuiliang,Hou, Haoqing
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- Molecular Tectonics: Design of Enantiopure Luminescent Heterometallic Ir(III)-Cd(II) Coordination Network
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With the aim of combining luminescence and chirality in heterometallic Ir(III)-Cd(II) coordination networks, synthetic strategies for the formation of new Ir(III)-based chiral metallatectons ([Ir(dFppy)2(1)][PF6]), both as a racemic mixture of Δ and Λ enantiomers (rac-[Ir(dFppy)2(1)][PF6]) and as enantiopure complexes (Δ-[Ir(dFppy)2(1)][PF6] and Λ-[Ir(dFppy)2(1)][PF6]), were developed. The final compounds were characterized both in solution and in the crystalline phase. Notably, their crystal structures were determined by single crystal X-ray diffraction, and their photophysical properties in solution and in the solid state were investigated. Combination of the cationic linear metallatecton with Cd2+ iodide salt ([CdI3]-), behaving as an anionic two-connecting node, leads to the formation of 1D chiral and neutral heterometallic Ir(III)-Cd(II) luminescent coordination networks both as a racemic mixture and as enantiomerically pure infinite architectures. The latter have been structurally studied in the solid state by X-ray diffraction both on single crystals and on microcrystalline powders. The infinite coordination networks display phosphorescence in the solid state at ca. 600 nm upon excitation at 400 nm.
- Xu, Chaojie,Guenet, Aurélie,Kyritsakas, Nathalie,Planeix, Jean-Marc,Hosseini, Mir Wais
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- π-conjugated chelating polymers with charged iridium complexes in the backbones: Synthesis, characterization, energy transfer, and electrochemical properties
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A series of π-conjugated chelating polymers with charged iridium (Ir) complexes in the backbones were synthesized by a Suzuki polycondensation reaction, leading to homogeneous polymeric materials that phosphoresce red light. The fluorene and bipyridine (bpy) segments were used as polymer backbones. 5.5′-Dibromobipyridine served as a ligand to form a charged iridium complex monomer with 1-(9′9-dioctylfluorene-2-yl)isoquinoline (Fiq) as the cyclometalated ligand. Chemical and photophysical characterization confirmed that Ir complexes were incorporated into the backbones as one of the repeat units by means of the 5.5′-dibromobipyridine ligand. Chelating polymers showed almost complete energy transfer from the host fluorene segments to the guest Ir complexes in the solid state when the feed ratio was 2 mol%. In the films of the corresponding blend system, however, energy transfer was not complete even when the content of Ir complexes was as high as 16 mol%. Both intra- and in termolecular energy-transfer processes existed in this host-guest system, and the intramolecular energy transfer was a more efficient process. All chelating polymers displayed good thermal stability, redox reversibility, and film formation. These chelating polymers also showed more efficient energy transfer than the corresponding blended system and the mechanism of incorporation of the charged Ir complexes into the π-conjugated polymer backbones efficiently avoided the intrinsic problems associated with the blend system, thus offering promise in optoelectronic applications.
- Liu, Shu-Juan,Zhao, Qiang,Chen, Run-Feng,Deng, Yun,Fan, Qu-Li,Li, Fu-You,Wang, Lian-Hui,Huang, Chun-Hui,Huang, Wei
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- Synthesis of Nitrile-Functionalized Polydentate N-Heterocycles as Building Blocks for Covalent Triazine Frameworks
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Covalent triazine frameworks (CTFs) based on polydentate ligands are highly promising supports to anchor catalytic metal complexes. The modular nature of CTFs allows to tailor the composition, structure, and function to its specific application. Access to a broad range of chelating building blocks is therefore essential. In this respect, we extended the current available set of CTF building blocks with new nitrile-functionalized N-heterocyclic ligands. This paper presents the synthesis of the six ligands which vary in the extent of the aromatic system and the denticity. The new building blocks may help in a rational design of enhanced support materials in catalysis.
- Debruyne, Maarten,Everaert, Jonas,Heugebaert, Thomas S. A.,Stevens, Christian V.,Van Der Voort, Pascal,Van Hecke, Kristof,Van Speybroeck, Veronique,Vanden Bussche, Flore
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- Cu(ii)Cl2containing bispyridine-based porous organic polymer support preparedviaalkyne-azide cycloaddition as a heterogeneous catalyst for oxidation of various olefins
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A new type of porous organic polymer (POP) based heterogeneous catalystCu-POPwas prepared by immobilizing Cu(ii)Cl2into bpy containing POP preparedviaalkyne-azide cycloaddition. This new catalyst showed efficient catalytic activities and outstanding reusability. Remarkably, one batch ofCu-POPwas continuously used for all olefins without losing its activity by simply washing.
- Choi, Hye Min,Lee, Suk Joong,Yoon, Jongho
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supporting information
p. 9149 - 9152
(2020/06/17)
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- Fundamentally Different Distance Dependences of Electron-Transfer Rates for Low and High Driving Forces
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The distance dependences of electron-transfer rates (kET) in three homologous series of donor-bridge-acceptor compounds with reaction free energies (ΔGET0) of ca. -1.2, -1.6, and -2.0 eV for thermal charge recombination after initial photoinduced charge separation were studied by transient absorption spectroscopy. In the series with low driving force, the distance dependence is normal and kET decreases upon donor-acceptor distance (rDA) elongation. In the two series with higher driving forces, kET increases with increasing distance over a certain range. This counterintuitive behavior can be explained by a weakly distance-dependent electronic donor-acceptor coupling (HDA) in combination with an increasing reorganization energy (λ). Our study shows that highly exergonic electron transfers can have distance dependences that differ drastically from those of the more commonly investigated weakly exergonic reactions.
- Neumann, Svenja,Wenger, Oliver S.
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supporting information
p. 855 - 860
(2019/01/11)
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- ELECTROCHROMIC COMPOUNDS AND OPTICAL ARTICLES CONTAINING THEM
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The present invention relates to a group of novel electrochromic compounds. More specifically, it relates to electrochromic compounds comprising one or several pyridinium rings and the use of these compounds as a variable transmittance medium for the manufacture of an optical article, such as an ophthalmic lens.
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- Merging Photoredox and Organometallic Catalysts in a Metal–Organic Framework Significantly Boosts Photocatalytic Activities
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Metal–organic frameworks (MOFs) have been extensively used for single-site catalysis and light harvesting, but their application in multicomponent photocatalysis is unexplored. We report here the successful incorporation of an IrIII photoredox catalyst and a NiII cross-coupling catalyst into a stable Zr12 MOF, Zr12-Ir-Ni, to efficiently catalyze C?S bond formation between various aryl iodides and thiols. The proximity of the IrIII and NiII catalytic components to each other (ca. 0.6 nm) in Zr12-Ir-Ni greatly facilitates electron and thiol radical transfers from Ir to Ni centers to reach a turnover number of 38 500, an order of magnitude higher than that of its homogeneous counterpart. This work highlights the opportunity in merging photoredox and organometallic catalysts in MOFs to effect challenging organic transformations.
- Zhu, Yuan-Yuan,Lan, Guangxu,Fan, Yingjie,Veroneau, Samuel S.,Song, Yang,Micheroni, Daniel,Lin, Wenbin
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supporting information
p. 14090 - 14094
(2018/10/15)
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- A contains the bipyridyl structure of aromatic diamine and its synthetic method
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The invention discloses aromatic diamine containing a bipyridine structure, and a synthetic method therefor. A chemical structural formula of the aromatic diamine is as shown in formula (1). The aromatic diamine containing a bipyridine unit prepared by the synthetic method is a novel diamine monomer containing the bipyridine unit; compared with a similar monomer containing a benzene ring, the aromatic diamine, which is used as a monomer containing a nitrogen heterocyclic ring, improves the performance of PI obtained by polymerization more remarkably, wherein the thermal stability and the glass transition temperature of the polymer are improved, and dielectricity of the polymer is remarkably improved. In a word, the aromatic diamine disclosed by the invention is more beneficial for improving the application processing performance of the polyimide and polyamide, and expanding the application field of the polyimide and polyamide.
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Paragraph 0024; 0026; 0027; 0030; 0033; 0036
(2018/09/12)
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- Preparation of a bispyridine based porous organic polymer as a new platform for Cu(ii) catalyst and its use in heterogeneous olefin epoxidation
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A new type of bispyridine (bpy) incorporated POP was prepared via a cobalt-catalyzed acetylene trimerization. Subsequent immobilization of CuCl2 gave POP-Cu(ii). This new heterogeneous catalyst displayed outstanding olefin oxidation activity compared to its homogeneous analogue, suggesting that the degradation of the homogeneous catalyst was successfully inhibited by site isolation.
- Yi, Jigyoung,Ahn, Hye Mi,Yoon, Jong Ho,Kim, Cheal,Lee, Suk Joong
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supporting information
p. 14067 - 14070
(2018/08/28)
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- Method for preparing 2,2'-bipyridine and its derivatives
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The invention discloses a method for preparing 2,2'-bipyridine and its derivatives. The method is characterized in that the 2,2'-bipyridine represented by formula II is generated through dehydrogenation coupling of pyridine represented by formula I, or its derivative, in the presence of an additive under the action of a supported catalyst, wherein R in the formula I and the formula II is H, a C1-C2 alkyl group, Cr or Br. The method has the advantages of extensive applicability of the raw material, high atom utilization rate, and high activity, long life and few byproducts in the catalyst.
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Paragraph 0049; 0051
(2018/06/15)
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- ORGANIC COMPOUND AND LIGHT EMITTING DIODE AND ORGANIC LIGHT EMITTING DIODE DISPLAY DEVICE USING THE SAME
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The present invention relates to an organic compound having excellent hole injection properties and charge generation properties by substituting an electron withdrawing group (Electron acceptor) for a conjugated bipyridine derivative core, to a light-emitting diode applying the organic compound to at least one organic layer, and to a display device.COPYRIGHT KIPO 2017
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Paragraph 0231-0234
(2017/08/18)
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- A phosphorescent iridium complex and its preparation method and application
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The invention relates to a phosphorescent iridium complex, and a preparation method and an application thereof, belongs to the technical field of organic photoelectric functional materials, and concretely relates to a preparation method of phosphorescent iridium complex molecules, and an application of the phosphorescent iridium complex molecules in molecule oxygen detection, and cell marking and imaging. The above complex material is composed of a cyclomedtalating ligand, a metal center and a benzyl substituted anthracene auxiliary ligand, has a structural general formula shown in the specification, has the advantages of long luminescence life, mild reaction conditions and easy purification, and has very good application prospects in anoxybiotic detection, cell imaging and pathology diagnosis.
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Paragraph 0035; 0036
(2017/08/25)
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- A highly efficient red-emitting ruthenium complex with 3,5-difluorophenyl substituents
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Five 3,5-difluorophenyl-substituted ruthenium complexes [Ru(bpy)2(dfpbpy)(ClO4)2] (Ru-Fbpy-bpy; bpy=bipyridine, dfpbpy=5,5′-di(3,5-difluorophenyl)-2,2′-bipyridine), [Ru(dpp)2(dfpbpy)(ClO4)2] (Ru-Fbpy-dpp; dpp=4,7-diphenyl-1,10-phenanthroline), [Ru(dpp)2(dfpphen)(ClO4)2] (Ru-Fphen-dpp; dfpphen=5,5′-di(3,5-difluorophenyl)-1,10-phenanthroline), [Ru(dpp)2(4,7-dfpphen)(ClO4)2] (Ru-Fdpp-dpp; 4,7-dfpphen=4,7-di(3,5-difluorophenyl)-1,10-phenanthroline), and [Ru(4,7-dfpphen)3(AsF6)2] (Ru-Fdpp) were synthesized, and their photophysical, electrochemical, and electroluminescent properties were studied systematically. The introduction of the electron-withdrawing group 3,5-difluorophenyl leads to a redshift of the emission of the ruthenium complexes. In addition, the 3,5-difluorophenyl substituent extends the π conjugation of the ligand, and thus facilitates the metal-to-ligand charge-transfer process of the complexes. All the complexes display orange-red phosphorescent emissions centered at 638, 638, 624, 614, and 605 nm, respectively. Density functional theory calculations show that the lowest unoccupied molecular orbital of Ru-Fbpy-dpp, Ru-Fphen-dpp, and Ru-Fdpp-dpp are all distributed on the 3,5-difluorophenyl-substituted ligand. By using these complexes as emitters, highly luminescent single-layer devices are obtained. The optimized device based on Ru-Fdpp exhibits the highest luminous efficiency and power efficiency of 4.19 cd A-1 and 1.46 lm W-1, respectively. Bright ideas: Five 3,5-difluorophenyl-substituted ruthenium complexes have been synthesized and characterized. The photoluminescent efficiencies of the complexes improved after introduction of an electron-withdrawing substituent (see scheme). The complexes are suitable as dopant light-emitting materials for organic light-emitting diodes.
- Zhu, Yingying,Fei, Teng,Ma, Yuguang
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- BORON-CONTAINING COMPOUND
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PROBLEM TO BE SOLVED: To provide a boron-containing compound suitable as organic electronic device materials such as organic EL element materials and n-type semiconductors. SOLUTION: A boron-containing compound is produced by, for example, the following chemical reaction. SELECTED DRAWING: None COPYRIGHT: (C)2017,JPOandINPIT
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Paragraph 0052-0055
(2017/05/02)
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- BORON-CONTAINING COMPOUND
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PROBLEM TO BE SOLVED: To provide a boron-containing compound suitable as an organic electronic device material such as an organic EL element material and an n-type semiconductor. SOLUTION: The present invention provides a boron-containing compound having a specific structure. SELECTED DRAWING: None COPYRIGHT: (C)2017,JPOandINPIT
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Paragraph 0078; 0079-0081
(2018/10/10)
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- Site Isolation Leads to Stable Photocatalytic Reduction of CO2 over a Rhenium-Based Catalyst
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A porous organic polymer incorporating [(α-diimine)Re(CO)3Cl] moieties was produced and tested in the photocatalytic reduction of CO2, with NEt3 as a sacrificial donor. The catalyst generated both H2 and CO, although the Re moiety was not required for H2 generation. After an induction period, the Re-containing porous organic polymer produced CO at a stable rate, unless soluble [(bpy)Re(CO)3Cl] (bpy=2,2′-bipyridine) was added. This provides the strongest evidence to date that [(α-diimine)Re(CO)3Cl] catalysts for photocatalytic CO2 reduction decompose through a bimetallic pathway.
- Liang, Weibin,Church, Tamara L.,Zheng, Sisi,Zhou, Chenlai,Haynes, Brian S.,D'Alessandro, Deanna M.
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supporting information
p. 18576 - 18579
(2016/01/25)
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- Molecular tectonics: Heterometallic (Ir,Cu) grid-type coordination networks based on cyclometallated Ir(III) chiral metallatectons
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A chiral-at-metal Ir(iii) organometallic metallatecton was synthesised as a racemic mixture and as enantiopure complexes and combined with Cu(ii) to afford a heterobimetallic (Ir,Cu) grid-type 2D coordination network.
- Xu, Chaojie,Guenet, Aurélie,Kyritsakas, Nathalie,Planeix, Jean-Marc,Hosseini, Mir Wais
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p. 14785 - 14788
(2015/10/05)
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- Isomer Dependence of Efficiency and Charge Recombination in Dye-Sensitized Solar Cells Using Ru Complex Dyes Bearing Halogen Substituents
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We have synthesised Ru(H2-dcbpy)(N,N′-Y2-bpy)(NCS)2 dyes (where N = 4, 5; Y = F, Cl, Br; N is the position on the bipyridyl ring where the halogen substituent is located) for dye-sensitised solar cells. We show that careful consideration of the position of the substituent, in conjunction with the nature of the substituents, on a bpy ring is important to optimize the solar cells performance. Changing the position (from 4,4′ to 5,5′) along with the nature of the halogen (F, Cl, or Br) substituents were observed to cause changes in the electronic and spectroscopic properties of the dyes as well as influence the recombination rates at the TiO2-dyes-I-/I3- interface affecting the performance of the dyes in DSSCs. Changing the position (from 4,4′ to 5,5′) along with the nature of the halogen (F, Cl, or Br) substituents affects the electronic and spectroscopic properties of the Ru(H2-dcbpy)(N,N′-Y2-bpy)(NCS)2 dyes as well as the recombination rates at the TiO2-dyes-I-/I3- interface hence affecting the performance of the dyes in DSSCs.
- Chadwick, Nina,Kumar, D. Kishore,Ivaturi, Aruna,Grew, Benjamin A.,Upadhyaya, Hari M.,Yellowlees, Lesley J.,Robertson, Neil
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p. 4878 - 4884
(2015/11/02)
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- SEPARATION OF NANOPARTICLES
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This invention is directed to separation, optimization and purification of nano-materials using self-assembled perylene diimide membranes, wherein said perylene diimide membrane is recyclable.
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(2013/11/19)
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- A study on the BF3 directed lithiation of 3-chloro- and 3-bromopyridine
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The BF3-directed lithiation of 3-chloro- and 3-bromopyridine (1a and 1b, respectively) has been investigated. The reactions of 3-chloro- or 3-bromopyridine-BF3 adduct with LDA (1.3/1.1 equiv) followed by quenching with benzaldehyde or iodine exclusively gave the C-2 substituted products. However, when 2.2 equiv of LDA and dimethyl disulfide was used, a C-6 substituted product was obtained. Dilithiation of 1a and 1b has been studied with and without the involvement of BF3 complexation. The role of Lia?F(BF3) interactions has been investigated by experimental and DFT calculations.
- Dhau, Jaspreet S.,Singh, Amritpal,Kasetti, Yoganjaneyulu,Bhatia, Sonam,Bharatam, Parsad V.,Brand?o, Paula,Félix, Vítor,Singh, Kamal N.
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p. 10284 - 10291
(2013/11/19)
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- Pentameric circular iron(II) double helicates and a molecular pentafoil knot
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We report on the synthesis of 11 pentameric cyclic helicates formed by imine condensation of alkyl monoamines with a common bis(formylpyridine) bipyridyl-derived building block and iron(II) and chloride ions. The cyclic double-stranded helicates were characterized by NMR spectroscopy, mass spectrometry, and in the case of a 2,4-dimethoxybenzylamine-derived pentameric cyclic helicate, X-ray crystallography. The factors influencing the assembly process (reactant stoichiometry, concentration, solvent, nature and amount of anion) were studied in detail: the role of chloride in the assembly process appears not to be limited to that of a simple template, and larger circular helicates observed with related tris(bipyridine) ligands with different iron salts are not produced with the imine ligands. Using certain chiral amines, pentameric cyclic helices of single handedness could be isolated and the stereochemistry of the helix determined by circular dichroism. By employing a particular diamine, a closed-loop molecular pentafoil knot was prepared. The pentafoil knot was characterized by NMR spectroscopy, mass spectrometry, and X-ray crystallography, confirming the topology and providing insights into the reasons for its formation.
- Ayme, Jean-Francois,Beves, Jonathon E.,Leigh, David A.,McBurney, Roy T.,Rissanen, Kari,Schultz, David
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supporting information; scheme or table
p. 9488 - 9497
(2012/07/14)
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- A copper-based shuttling [2]rotaxane with two bidentate chelates in the axis: Steric control of the motion
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Contrary to most of the other molecular machines based on copper-complexed catenanes or rotaxanes made and investigated in Strasbourg, the present report is dealing with a molecular shuttle for which the copper centre is complexed to two bidentate chelates, regardless of the state of the shuttle. In other words, the axis contains a sterically hindering bidentate chelate, namely a 2,9-diphenyl-1,10-phenanthroline (dpp) derivative, and another but less hindering bidentate chelate, 2,2′-bipyridine (bipy). The synthesis of the [2]rotaxane involves 15 individual chemical steps, excluding the preparation of the macrocyclic component of the [2]rotaxane. The threaded macrocycle is a 39-membered ring which incorporates an endocyclic but non sterically hindering chelate of the 8,8′-diphenyl-3,3′-biisoquinoline family (dpbiiq). The electrochemically-induced gliding motion of the copper-complexed ring from the dpp "station" to the bipy "station" and vice versa is fast on the cyclic voltammetry timescale (milliseconds). The copper(i) state is preferably located on the dpp unit whereas, by oxidising the copper(i) centre to its divalent state, the translation motion takes place to afford the thermodynamically most stable state now involving the bipy chelate.
- Collin, Jean-Paul,Durola, Fabien,Lux, Jacques,Sauvage, Jean-Pierre
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experimental part
p. 34 - 43
(2011/01/06)
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- COMPOUND HAVING SUBSTITUTED PYRIDYL GROUP AND PYRIDOINDOLE RING STRUCTURE LINKED THROUGH PHENYLENE GROUP, AND ORGANIC ELECTROLUMINESCENT DEVICE
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Objects of the present invention are to provide an organic compound having excellent properties, which is excellent in electron-injecting/transporting performances, has hole-blocking ability and is highly stable in a thin-film state, as a material for an organic electroluminescent device having a high efficiency and a high durability; and to provide an organic electroluminescent device having a high efficiency and a high durability using the compound. The invention relates to a compound having a substituted pyridyl group and a pyridoindole ring structure linked through a phenylene group, which is represented by the general formula (1); and an organic EL device comprising a pair of electrodes and at least one organic layer interposed between the electrodes, wherein the at least one organic layer contains the compound: wherein Ar represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group; R1 to R14 may be the same or different from each other and each represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a linear or branched alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group; n represents an integer of 1 to 3; and W, X, Y, and Z respectively represent a carbon atom or a nitrogen atom, provided that only one of W, X, Y, and Z represents a nitrogen atom, and the nitrogen atom does not have the substituent of R7, R8, R9, or R10).
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Page/Page column 43
(2010/11/03)
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- A rapidly shuttling copper-complexed [2]rotaxane with three different chelating groups in its axis
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Fast and furious: The mobile ring of a copper-complexed [2]rotaxane incorporates an endocyclic but nonsterically hindering bidentate chelate. The rotaxane axis contains three different chelates (see picture), and both terminal coordination sites are separ
- Collin, Jean-Paul,Durola, Fabien,Lux, Jacques,Sauvage, Jean-Pierre
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supporting information; experimental part
p. 8532 - 8535
(2009/12/26)
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- DOUBLY REDUCED PERYLENE-DIIMIDES AND SUPRAMOLECULAR POLYMERS DERIVED FROM PERYLENE-DIIMIDES
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This invention is directed to perylene-diimide aromatic dianion compounds, process of preparation and uses thereof. The perylene-diimide aromatic dianion compounds of this invention are stable in aqueous solution and can be used for photofunctional and electron transfer systems in aqueous phase. This invention is also directed to supramolecular polymers derived from perylene-diimide compounds and to uses thereof. (1)wherein said compound is a dianion; wherein, X is - NR1; Y is - NR2;
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- Efficient catalytic systems for synthesis of 5,5″-dibromo-2,2′: 6′,2″-terpyridine and 5, 5′-dibromo-2, 2prime;-bipyridine via coupling of dihalogenopyridines with 5-bromo-2-trialkylstannylpyridines
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The results of the studies on the synthesis of 5,5′-dibromo-2, 2′-bipyridine and 5,5″-di-bromo-2,2′:6′,2″- terpyridine via coupling of 5-bromo-2-iodopyridine and 2,6-dihalo-genopyridines with 5-bromo-2-trialkylstannylpyridines mediated by palladium catalysts have been presented. The catalytic activity of the Pd(II) and Pd(0) complexes (e.g. [PdC12(PPh3)2], [PdCl2(COD)], [Pd(dba)2]), and catalytic systems generated in situ from a stable precursor (e.g. [PdC12], [Pd(acac)2]) and an external ligand (APh3, where A = P, As, Sb; phosphines, phosphites) in the coupling of diiodopyridine with 5-bromo-2-tributylstannylpyridine was investigated. The most active system was that generated from [Pd(acac) 2] and P(OPh)3, while the highest coupling selectivity was achieved with [Pd(acac)2] and PPh3. The catalytic activity of systems containing chelating ligands BINAP or dppf was slightly inferior. In all reactions the formation of 5,5′-dibromo-2,2′- bipyridine, the product of homocoupling of 5-bromo-2-tributylstannylpyridine, was observed. An increase of the L/Pd ratio for catalytic system generated from [Pd(acac)2] and P(OPh)3 resulted in improved selectivity of dbtpy formation (the yield of dbbpy, the product of homocoupling, decreased) and in an increased stability of the catalytic system (without decreasing the reaction rate even for Pd/L = 1:32). On the other hand, for the systems containing phosphines the increase of L/Pd above 4:1 for mono- dentate phosphines and above 2:1 for bidentate phosphines resulted in a fast decrease of the reaction rate. The coupling is faster for 2,6-diiodopyridine and slower for 2,6-dibromopyridine, while 2,6-dichIoropyridine is nonreactive. The yield of coupling for trimethyl- and tributylstannyl derivatives is practically identical. Particularly advantageous solvents for the studied coupling reaction are xylene, toluene, and 1,2-diethoxyethane.
- Krompiec,Ignasiak,Krompiec,Stanek,Filapek,Gebarowska,Penczek
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p. 245 - 262
(2009/10/09)
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- Cruciform oligo(phenylenevinylene) with a bipyridine bridge: Synthesis, its rhenium(I) complex and photovoltaic properties
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A cruciform-shaped oligo(phenylenevinylene) (OPV) with a phosphorescent rhenium(I) chromophore incorporated at the centre and grafted triphenylamines around the periphery was designed as a new organic photovoltaic material, in which the chelation of rhenium(I) to the cruciform successfully constructs a three-dimensional intramolecular charge transfer system and extends the exciton lifetime; as a result, the rhenium-OPV complex shows a power conversion efficiency almost two times that of the metal ion-free parent compound. The Royal Society of Chemistry.
- He, Feng,Zhou, Yinhua,Liu, Suijun,Tian, Leilei,Xu, Hai,Zhang, Houyu,Yang, Bin,Dong, Qingfang,Tian, Wenjing,Ma, Yuguang,Shen, Jiacong
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body text
p. 3912 - 3914
(2009/02/07)
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- Preparation of novel substituted haloarene compounds
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This invention relates to a new process for the preparation of novel substituted haloarene compounds of the formula I or IV: respectively, wherein R1, R2, R3, R4, R5, X, and Y are as defined herein, that comprises a novel and efficient selective mono-lithiation of a dihaloarene of the formula II or V: respectively, by an organo-lithium compound in the presence of a carbonyl reactant of the formula III: wherein R1 and R2 are as defined herein. In the process of the instant invention, the newly formed lithiated haloarene is sequentially quenched in situ by the carbonyl reactant to form said substituted haloarene. The process is suitable for batch or continuous flow systems. The substituted haloarenes produced by the process of the present invention are useful intermediates in the preparation of N-aryl or N-heteroaryl substituted pharmaceutically active compounds that include selective antagonists, inverse agonists and partial agonists of serotonin 1 (5-HT1) receptors useful in treating or preventing depression, anxiety, obsessive compulsive disorder (OCD) and other disorders for which a 5-HT1 agonist or antagonist is indicated.
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(2008/06/13)
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- Synthesis of a linear bis-porphyrin with a Ru(phen)22+-complexed 2,2′-bipyridine spacer
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A linear bis-porphyrin bridged by a 5,5′-diphenyl-2,2′-bipyridine rod-like spacer complexing a [Ru(phen)2]2+ fragment has been synthesized in 7.4% yield by one-pot condensation of 3,5-di-tert-butylbenzaldehyde, 4,4′-dimethyl-3,3′-dihexyl-2,2′-methylenedipyrrole and the [Ru(phen)2]2+ complex of 5,5′-bis(p-formylphenyl)-2,2′-bipyridine, followed by chloranil oxidation. The protected dialdehyde (5,5′-bis[(5,5-dimethyl-1,3-dioxan-2-yl)phenyl]-2,2′-bipyridine) was obtained in 80% yield by Suzuki coupling of 2-[4-(5,5-dimethyl-1,3-dioxan-2-yl)phenyl]-4,4,5,5-tetramethyl-1, 3-dioxaborolane and 5,5′-dibromo-2,2′-bipyridine, using [Pd(PPh3)4] as catalyst. A new procedure is reported for the preparation of 5,5′-dibromo-2,2′-bipyridine, which is obtained in 80% yield by Stille homocoupling of 2,5-dibromopyridine in the presence of hexamethylditin.
- Bruce, James I.,Chambron, Jean-Claude,Koelle, Philipp,Sauvage, Jean-Pierre
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p. 1226 - 1231
(2007/10/03)
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- Preparation of 5-brominated and 5,5′-dibrominated 2,2′-bipyridines and 2,2′-bipyrimidines
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Efficient syntheses of 5-brominated and 5,5′-dibrominated 2,2′-bipyridines and 2,2′-bipyrimidines, useful for the preparation of metal-complexing molecular rods, have been developed. 5-Bromo-2,2-bipyridine, 5-bromo-5′-n-butyl-2,2′-bipyridine, and 5-bromo-5′-n-hexyl-2,2′-bipyridine were obtained by Stille coupling of 2,5-dibromopyridine with 2-trimethylstannylpyridine or the requisite 5-alkyl-2-trimethylstannylpyridine, obtained via regioselective zincation of a 3-alkylpyridine. BF3 complex in the less hindered of the two reactive positions with lithium di-tert-butyl-(2,2,6,6-tetramethyl-piperidino)zincate. 5,5′-Dibromo-2,2′-bipyridine was obtained by the reductive symmetric coupling of 2,5-dibromopyridine with hexa-n-butyldistannane. The yields of these coupling reactions ranged from 70 to 90%. 5-Bromo- and 5,5′-dibromo-2,2′-bipyrimidines were obtained in yields of 30 and 15%, respectively, by bromination of 2,2′-bipyrimidine, prepared from 2-chloropyrimidine in 80% yield by an improved reductive symmetric coupling procedure.
- Schwab, Peter F.H.,Fleischer, Frank,Michl, Josef
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p. 443 - 449
(2007/10/03)
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- 5,5″-disubstituted 2,2′:6′,2″-terpyridines through and for metal-mediated cross-coupling chemistry
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The 0.3-5 g scale syntheses of the 2,2′:6′,2″-terpyridines 3, 6, 9, and 10 are described. The pyridine units are connected to one another by Pd-catalyzed cross-coupling reactions. This method allows the easy introduction of halogen, stannyl, and boronic ester functionalities at positions C-5 and C-5″; this results in a novel functionality pattern for terpyridines that considerably widens the applicability of this class of tridentate ligands for supra- and macromolecular applications. The feasibility of growth reactions with these novel terpyridines was demonstrated by the synthesis of compounds 12a-c.
- Lehmann, Uwe,Henze, Oliver,Schlueter, A. Dieter
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p. 854 - 859
(2007/10/03)
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