- Graphite diyne film and preparation method and application thereof
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The invention relates to a graphite diyne film as well as a preparation method and application thereof. A precursor of the graphite diyne film is hexa(bromo-ethynyl) benzene. The method comprises the following steps: (1) injecting a solvent into a reactor filled with hexa(bromo-ethynyl) benzene and a copper-containing substrate; (2) dropwise adding an alkali solution into the reactor, stirring under the protection of an inert atmosphere, and carrying out a debromination coupling reaction; and (3) after the reaction is finished, generating a layer of black semitransparent film on the surface of the substrate, washing the surface of the substrate with acetone and N,N-dimethylformamide to obtain a black graphite diyne film which is applied to a catalytic material, an energy material or an electrode material. Compared with the prior art, the preparation method has the advantages that monomer molecules are more stable in air and higher in reaction activity, a coupling reaction can be stably and efficiently carried out, the reaction time is greatly shortened, the reaction can be carried out at room temperature, additional heating is not needed, energy can be greatly saved, and the problem of organic solvent volatilization caused by heating is solved.
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Paragraph 0042
(2021/09/04)
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- Self-assembly of radially π-extended tetrathiafulvalene tetramers for visible and near infrared electrochromic nanofiber
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The self-assembly and electrochromic nanofiber formation of radially 7pi;-extended tetrathiafulvalene (TTF) tetramers anchored to 1,2,4,5-tetraethynylbenzene were investigated. The tetramer with SBu-substituents underwent self-assembly in solution. Cationic species of the tetramer, obtained by chemical oxidation with Fe(ClO4)3, exhibited a marked electrochromism in the solution. Their electronic spectra revealed absorption bands corresponding to intermolecular mixed-valence aggregation based on (TTF//TTF)+, and π-aggregation based on (TTF?+//TTF?+) due to the strong molecular association in the cationic species. Furthermore, the tetramer formed an entangled nanoscale fibrous material from CHCl3 hexane. Electrochemical oxidation of the nanofiber on an indium tin oxide electrode revealed a repeatable redox profile. The nanofiber displayed remarkable electrochromic behavior: The color of the fiber changed from purple (neutral) to brown/brownish green (dication and trication) and green (tetracation). These color changes of the nanofiber are similar to those in solution, and the electronic spectra of the oxidized nanofibers reflected the stacked TTF units in the cationic nanofibers.
- Hasegawa, Masashi,Iyoda, Masahiko
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supporting information
p. 154 - 162
(2020/02/11)
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- Distinctive Improved Synthesis and Application Extensions Graphdiyne for Efficient Photocatalytic Hydrogen Evolution
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Graphdiyne (GD), a novel two-dimension carbon hybrid material, due to its unique and excellent properties, has been widely concerned since this innovative material was successfully synthesized by Prof. Yuliang Li in 2010. Traditionally, its synthesis method is growing graphdiyne on copper foils or foam copper as a base catalytic material to deliver copper ions (Cu2+) under pyridine conditions. Here, an innovative progress for graphdiyne preparation approach of using Cu+ ion as a catalytic material is reported and its application in extending to the photocatalytic water-splitting to produce hydrogen in situ as well. In detail, by means of cuprous iodide used as a catalyst-carrier to grow a graphdiyne in a pyridine solution of monomeric hexynylbenzene and such CuI-graphdiyne composite catalyst is directly applied to photocatalytic hydrogen production in situ. Meanwhile, the hydrogen production of GD and CuI are 29.42 μmol/5 h and 156.49 μmol/5 h, respectively. In particular, the composite catalyst GD-CuI exhibits an optimum photo-catalytic hydrogen production activity (465.95 μmol/5 h) which is 15.8 times and 3.0 times that of pure GD and CuI respectively. This rational design, one-step construction of GD-CuI, successfully enhances photo-catalytic hydrogen evolution activity. The deeper characterization study results such as TEM, SEM, XPS, XRD, UV-vis DRS, Transient photocurrent and FT-IR etc. have been well researched and the results of which are in good agreement with each other.
- Li, Yanbing,Yang, Hao,Wang, Guorong,Ma, Bingzhen,Jin, Zhiliang
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p. 1985 - 1995
(2020/02/13)
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- Synthesis and Crystal Structure of Dimorphic Dibenzo[cde,opq]rubicene
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Dibenzo[cde,opq]rubicene has been synthesized by an eight-step reaction sequence including an iron-mediated [2+2+1] cycloaddition and a flash vacuum pyrolysis as key steps. Two crystal modifications of the S-shaped, planar polycyclic aromatic hydrocarbon have been obtained and characterized by X-ray diffractometry.
- Suresh, Joghee R.,Whitener, Glenn,Theumer, Gabriele,Br?cher, Dirk J.,Bauer, Ingmar,Massa, Werner,Kn?lker, Hans-Joachim
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p. 13759 - 13765
(2019/11/03)
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- Fluorescent Sulphur- and Nitrogen-Containing Porous Polymers with Tuneable Donor–Acceptor Domains for Light-Driven Hydrogen Evolution
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Light-driven water splitting is a potential source of abundant, clean energy, yet efficient charge-separation and size and position of the bandgap in heterogeneous photocatalysts are challenging to predict and design. Synthetic attempts to tune the bandgap of polymer photocatalysts classically rely on variations of the sizes of their π-conjugated domains. However, only donor–acceptor dyads hold the key to prevent undesired electron-hole recombination within the catalyst via efficient charge separation. Building on our previous success in incorporating electron-donating, sulphur-containing linkers and electron-withdrawing, triazine (C3N3) units into porous polymers, we report the synthesis of six visible-light-active, triazine-based polymers with a high heteroatom-content of S and N that photocatalytically generate H2 from water: up to 915 μmol h?1 g?1 with Pt co-catalyst, and—as one of the highest to-date reported values ?200 μmol h?1 g?1 without. The highly modular Sonogashira–Hagihara cross-coupling reaction we employ, enables a systematic study of mixed (S, N, C) and (N, C)-only polymer systems. Our results highlight that photocatalytic water-splitting does not only require an ideal optical bandgap of ≈2.2 eV, but that the choice of donor–acceptor motifs profoundly impacts charge-transfer and catalytic activity.
- Schwarz, Dana,Acharja, Amitava,Ichangi, Arun,Lyu, Pengbo,Opanasenko, Maksym V.,Go?ler, Fabian R.,K?nig, Tobias A. F.,?ejka, Ji?í,Nachtigall, Petr,Thomas, Arne,Bojdys, Michael J.
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supporting information
p. 11916 - 11921
(2018/08/21)
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- Intermolecular On-Surface σ-Bond Metathesis
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Silylation and desilylation are important functional group manipulations in solution-phase organic chemistry that are heavily used to protect/deprotect different functionalities. Herein, we disclose the first examples of the σ-bond metathesis of silylated alkynes with aromatic carboxylic acids on the Ag(111) and Au(111) surfaces to give the corresponding terminal alkynes and silyl esters, which is supported by density functional theory calculations and further confirmed by X-ray photoelectron spectroscopy analysis. Such a protecting group strategy applied to on-surface chemistry allows self-assembly structures to be generated from molecules that are inherently unstable in solution and in the solid state. This is shown by the successful formation of self-assembled hexaethynylbenzene at Ag(111). Furthermore, it is also shown that on the Au(111) surface this σ-bond metathesis can be combined with Glaser coupling to fabricate covalent polymers via a cascade process.
- Gao, Hong-Ying,Held, Philipp Alexander,Amirjalayer, Saeed,Liu, Lacheng,Timmer, Alexander,Schirmer, Birgitta,Díaz Arado, Oscar,M?nig, Harry,Mück-Lichtenfeld, Christian,Neugebauer, Johannes,Studer, Armido,Fuchs, Harald
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supporting information
p. 7012 - 7019
(2017/05/31)
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- Tailored Band Gaps in Sulfur- and Nitrogen-Containing Porous Donor–Acceptor Polymers
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Donor–acceptor dyads hold the key to tuning of electrochemical properties and enhanced mobility of charge carriers, yet their incorporation into a heterogeneous polymer network proves difficulty owing to the fundamentally different chemistry of the donor and acceptor subunits. A family of sulfur- and nitrogen-containing porous polymers (SNPs) are obtained via Sonogashira–Hagihara cross-coupling and combine electron-withdrawing triazine (C3N3) and electron-donating, sulfur-containing linkers. Choice of building blocks and synthetic conditions determines the optical band gap (from 1.67 to 2.58 eV) and nanoscale ordering of these microporous materials with BET surface areas of up to 545 m2 g?1 and CO2 capacities up to 1.56 mmol g?1. Our results highlight the advantages of the modular design of SNPs, and one of the highest photocatalytic hydrogen evolution rates for a cross-linked polymer without Pt co-catalyst is attained (194 μmol h?1 g?1).
- Schwarz, Dana,Kochergin, Yaroslav S.,Acharjya, Amitava,Ichangi, Arun,Opanasenko, Maksym V.,?ejka, Ji?í,Lappan, Uwe,Arki, Pal,He, Junjie,Schmidt, Johannes,Nachtigall, Petr,Thomas, Arne,Tarábek, Ján,Bojdys, Michael J.
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supporting information
p. 13023 - 13027
(2017/09/06)
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- Methods for the total chemical synthesis of enantiomerically-pure 7-(2′-trimethylsilyl)ethyl camptothecin
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The present invention discloses and claims five (5) novel, highly efficient synthetic routes for the total synthesis of enantiomerically-pure (i.e., 99%) 7-(2′-trimethylsilyl)ethyl camptothecin (BNP1350; Karenitecin; Cositecan). These aforementioned synthetic schemes are the first to disclose the total syntheses of 7-(2′-trimethylsilyl)ethyl camptothecin using a highly novel direct, non-linear and convergent synthetic strategy which involves annealing the key C7-(trimethylsilyl)ethyl side chain-bearing A ring key synthons to an enantiomerically-pure tricyclic pyridone; rather than through the conventional methodology which incorporates the C7-(trimethylsilyl)ethyl side chain as the final synthetic step on a totally synthesized camptothecin parent compound. The current novel synthetic approaches reported herein since utilize desirably functionalized A-ring with preinstalled trimethyl silyl ethyl side chain, the aforementioned synthetic methodologies have a wider scope of making wide range of pharmaceutically relevant A-ring substituted BNP1350 analogs by substituting desirably functionalized nitro or protected amino phenyl carboxy A-ring as the starting material.
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Page/Page column 22
(2014/05/20)
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- Bent-core luminescent and electroactive bis(triazolyl)triazines with compact columnar mesomorphism
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The bulk self-assembly of bent-core molecules based on the novel structure 2-methoxy-4,6-bis(1′,2′,3′-triazol-4′-yl)-1,3, 5-triazine is reported together with their luminescent and electrochemical properties. Two families of compounds with lateral branches of different lengths have been investigated. Columnar mesomorphism with short stacking distances and periodic twisted structures were found. A compound exhibiting two hexagonal columnar mesophases that show different emission spectra and a transition from a bimolecular assembly to a unimolecular assembly is described.
- Beltran, Eduardo,Robles-Hernandez, Beatriz,Sebastian, Nerea,Serrano, Jose Luis,Gimenez, Raquel,Sierra, Teresa
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p. 23554 - 23561
(2014/07/07)
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- Direct arylations for study of the air-stable p-heterocyclic biradical: From wide electronic tuning to characterization of the localized radicalic electrons
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We have developed methods for installing aryl substituents directly on the phosphino groups of the 1,3-diphosphacyclobutane-2,4-diyl system. The aryl substituents tuned the electronic and structural characteristics of the biradical unit both in solution and in the solid state. 1-tert-butyl-2,4-bis(2, 4,6-tri-tert-butylphenyl)-1,3-diphosphacyclobuten-4-yl anion, prepared from phosphaalkyne (MesCi - P; Mes* = 2,4,6-tBu3C 6H2) and t-butyllithium, was allowed to react with an electron-deficient N-heterocyclic reagent. The corresponding N-heteroaryl-substituted P-heterocyclic biradicals were produced via S NAr reactions. Biradicals bearing perfluorinated pyridyl substituents exhibited photoabsorption properties comparable to those of previously reported derivatives because the highest occupied and lowest unoccupied molecular orbit levels were reduced by a similar amount. In contrast, the triazine substituent reduced the band gap of the biradical unit, and the large red shift in the visible absorption and high oxidation potential were further tuned via subsequent SNAr and Negishi coupling reactions. The amino-substituted triazine structure provided a strongly electron-donating biradical chromophore, which produced unique p-type semiconducting behavior even though there was no obvious π-overlap in the crystalline state. The single-electron transfer reaction involving Mes Ci - P, phenyllithium, and iodine afforded 1,3-diphenyl-2,4-bis(2,4,6-tri-tert-butylphenyl)-1,3-diphosphacyclobutane-2, 4-diyl via the intermediate P-heterocyclic monoradical. The tetraaryl- substituted symmetric biradical product was used to determine the electron density distribution from the X-ray diffraction data. The data show highly localized radicalic electrons around the skeletal carbon atoms, moderately polarized skeletal P-C bonds in the four-membered ring, and no covalent transannular interaction.
- Ito, Shigekazu,Ueta, Yasuhiro,Ngo, Trang Thi Thu,Kobayashi, Makoto,Hashizume, Daisuke,Nishida, Jun-Ichi,Yamashita, Yoshiro,Mikami, Koichi
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supporting information
p. 17610 - 17616
(2014/01/06)
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- Synthesis of α-amino amides via N,O-acetals derived from Weinreb amides
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(Chemical Equation Presented) An easy and straightforward synthesis of α-amino amides via a base-mediated rearrangement of modified Weinreb amides into N,O-acetals is presented. Subsequent arylation, alkylation, alkenylation, or alkynylation of this intermediate affords the corresponding R-amino amides in excellent yields. Furthermore, a more generalized protocol for the α-arylation of Weinreb amides lacking an R-amino moiety is also discussed.
- Hirner, Sebastian,Somfai, Peter
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supporting information; experimental part
p. 7798 - 7803
(2009/12/29)
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- Total synthesis of (±)-erythrocarine using dienyne metathesis
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Total Synthesis of (±)-erythrocarine was achieved using ruthenium-catalyzed dienyne metathesis as a key step. A tetrahydroisoquinoline skeleton having tetrasubstituted carbon center was constructed using our method, that is, carbon dioxide and an alkyl group were introduced onto an alkyne having a heteroatom in a tether using the nickel complex to produce α,β-unsaturated carboxylic acid and then isoquinoline skeleton was constructed by Michael reaction of the tethered nitrogen to the resultant α,β-unsaturated ester.
- Shimizu, Kazuya,Takimoto, Masanori,Sato, Yoshihiro,Mori, Miwako
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p. 5466 - 5475
(2007/10/03)
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- PROCESSES FOR PRODUCING POLY-ETHYNYL-SUBSTITUTED AROMATIC COMPOUND
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A process for preparing a poly-ethynyl-substituted aromatic compound characterized by reacting a halogenated benzene with an ethynylzinc halide; a process for preparing a poly-ethynyl-substituted aromatic compound characterized by using a halogenated benzene having at least two kinds of halogen atoms as a halogenated benzene, and (A) reacting one kind of the halogen atoms existing in the halogenated benzene with an ethynyl group-containing compound; and (B) reacting the other kind of halogen atoms remaining in the formed compound with an ethynylzinc halide. The poly-ethynyl-substituted aromatic compound is used as liquid crystals, nonlinear optical materials, electroconductive materials and the like
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Page column 7-8
(2010/02/05)
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- CONVENIENT SYNTHESIS OF (TRIPHENYL)GERMYL AND (TRIPHENYL)STANNYL SUBSTITUTED ALLENES
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Allenyl-germanes and -stannanes, Ph3MC(R)=C=CR'R" (M = Ge, Sn) can be obtained, generally in excellent yield, through alkylcopper(I)-induced 1,3-substitution of the propargylic chlorides Ph3MCCCR'R"Cl.In the tin series, however transmetallation is the
- Ruitenberg, K.,Westmijze, H.,Kleijn, H.,Vermeer, P.
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p. 227 - 234
(2007/10/02)
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