- Nanosized Molecular Propellers by Cyclodehydrogenation of Polyphenylene Dendrimers
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In a polymer analogous approach, large dendritic oligophenylenes containing benzene and tetraphenylmethane cores are transformed via oxidative cyclodehydrogenation to novel propeller-shaped molecules with large polycyclic aromatic hydrocarbon units as "bl
- Simpson, Christopher D.,Mattersteig, Gunter,Martin, Kai,Gherghel, Lileta,Bauer, Roland E.,Raeder, Hans Joachim,Muellen, Klaus
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- Reticular Synthesis of tbo Topology Covalent Organic Frameworks
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The metal-organic framework (MOF) HKUST-1 with a tbo topology serves as an archetypal tunable and isoreticular framework platform for targeting desired applications, but the design and synthesis of tbo-covalent organic frameworks (COFs) remains a formidable challenge. Here we demonstrate the successful use of reticular chemistry as an appropriate strategy for the design and deliberate construction of COFs with a tbo topology. The judicious selection of the perquisite planar building blocks, 4-connected square tetramine of porphyrin and 3-connected trigonal trialdehydes of triphenylamine, allows the condensation of two tbo-COFs, the first examples of COFs with a tbo topology. The resulting COFs both crystallize in the cubic Pm3ˉ space group and adopt a non-interpenetrated open framework, in which each tritopic linker connects to three square units forming a truncated Td-octahedron and occupies the alternating triangular faces of the truncated octahedron. Owing to the presence of two different types of photoredox-active moieties, the two COFs can be efficient heterogeneous photocatalysts for the oxidative hydroxylation of arylboronic acids and the reductive defluoroalkylation of trifluoromethyl aromatics with alkenes. The present finding will provide an impetus to examine the potential of tbo-COFs as a new platform for engineering multifunctional materials via expansion and functionalization of building blocks.
- Kang, Xing,Han, Xing,Yuan, Chen,Cheng, Cheng,Liu, Yan,Cui, Yong
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p. 16346 - 16356
(2020/10/26)
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- Preparation method and application of porphyrin polymer
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The invention belongs to the field of photo-Fenton catalysts, and particularly relates to a preparation method and application of a porphyrin polymer. A photo-Fenton catalyst used at present generallyneeds to be subjected to a catalytic reaction under ultraviolet light and acidic conditions, ultraviolet light irradiation and acid liquor need to be added for treatment, metal ion leaching can be accompanied in the catalytic process, and the environment is remarkably influenced. The invention provides a porous organic polymer based on metalloporphyrin. FePPOP-1 is synthesized through a Sonogashira cross coupling reaction of FeTBrPP and TEPB. The polymer has good stability, and compared with a traditional Fenton reaction, FePPOP-1 can still effectively degrade MB under the neutral condition that the pH value is equal to 7, and leaching of iron ions does not exist in the reaction process. The research result provides a research direction for the application of the metalloporphyrin porous organic polymer in the photo-Fenton catalyst.
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Paragraph 0078-0086
(2020/08/30)
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- Electronic Decoupling in C3-Symmetrical Light-Responsive Tris(Azobenzene) Scaffolds: Self-Assembly and Multiphotochromism
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We report the synthesis of a novel C3-symmetrical multiphotochromic molecule bearing three azobenzene units at positions 1, 3, 5 of the central phenyl ring. The unique geometrical design of such a rigid scaffold enables the electronic decouplin
- Galanti, Agostino,Diez-Cabanes, Valentin,Santoro, Jasmin,Valá?ek, Michal,Minoia, Andrea,Mayor, Marcel,Cornil, Jér?me,Samorì, Paolo
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p. 16062 - 16070
(2018/11/23)
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- Clicked isoreticular metal-organic frameworks and their high performance in the selective capture and separation of large organic molecules
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Three highly porous metal-organic frameworks (MOFs) with a uniform rht-type topological network but hierarchical pores were successfully constructed by the assembly of triazole-containing dendritic hexacarboxylate ligands with ZnII ions. These
- Li, Pei-Zhou,Wang, Xiao-Jun,Tan, Si Yu,Ang, Chung Yen,Chen, Hongzhong,Liu, Jia,Zou, Ruqiang,Zhao, Yanli
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supporting information
p. 12748 - 12752
(2015/10/28)
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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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- Modular syntheses of star-shaped pyridine, bipyridine, and terpyridine derivatives by employing sonogashira reactions
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A simple and flexible synthesis for a series of star-shaped pyridine, bipyridine, and terpyridine derivatives is reported by using a modular approach that combines the use of a ligand, spacer, and core unit. A fairly efficient method to prepare 4′-nonafloxy-functionalized terpyridine derivatives is described. The building blocks that contain the functionalized pyridine, bipyridine, or terpyridine derivatives were linked to different C3-symmetrical core units. In most cases, Sonogashira reactions were employed in the crucial final steps of the synthesis. A star-shaped dodecafluorinated compound was also prepared in a straightforward fashion. A simple procedure for the preparation of partially silylated 1,3,5-triethynylbenzene derivatives is presented, which provides an approach to C2-symmetrical star-shaped compounds that have only one terpyridine and two terphenyl units as "dummy" ligands. The absorption and emission spectra of the fully conjugated C3-symmetrical pyridine derivatives were systematically investigated, and fairly large Stokes shifts were observed.
- Trawny, Daniel,Kunz, Valentin,Reissig, Hans-Ulrich
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supporting information
p. 6295 - 6302
(2015/03/30)
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- Self-assembled supramolecular clusters based on phosphines and coinage metals: Tetrahedra, helicates, and mesocates
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An array of coordination-driven supramolecular metal-ligand clusters has been synthesized using polytopic phosphine ligands and coinage metals (Cu +, Ag+, Au+). Rigid 3-fold or 2-fold symmetric phosphine ligands have been prepared: 1,3,5-tris((4-(diphenylphosphino)ethynyl) phenyl)benzene) (tppepb, L1), 1,4-bis((diphenylphosphino)ethynyl) benzene (1,4-dppeb, L2), 1,3-bis((diphenylphosphino)ethynyl)benzene (1,3-dppeb, L3), 2,6-bis((diphenylphosphino)ethynyl)pyridine (2,6-dppep, L4), and 1,5-bis((diphenylphosphino)ethynyl)naphthalene (1,5-dppen, L5). Self-assembly of these ligands with coinage metals produces four different types of metal-ligand clusters, or in some cases coordination polymers, depending on number and relative geometry of the phosphine donor atoms. Supramolecular tetrahedral clusters of the formula M 4(L1)4I4 (M = Cu+, Ag+, Au+) were obtained with the tppepb ligand, encapsulating solvent molecules (either CH2Cl2 or DMF) as guests within the central cavity of the clusters. The ligands 1,3-dppeb (L 3) and 2,6-dppep (L4) give achiral, triple-stranded, dinuclear mesocates with the formula M2(L)3I2 (M = Cu+ or Au+). In contrast, the ligand 1,4-dppeb (L2) generates a triple-stranded, dinuclear helicate with Cu +, but a coordination polymer with Au+ (both with the empirical formula M2(L2)3I2). Finally, coordination polymers were obtained from 1,5-dppen (L5) with Cu+. The clusters have been fully characterized by single crystal X-ray crystallography, high-resolution mass spectrometry, 1H NMR, and 31P NMR.
- Lim, Sang Ho,Cohen, Seth M.
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p. 7862 - 7872
(2013/08/23)
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- 1,3,5-Triphenylbenzene fluorophore as a selective Cu2+ sensor in aqueous media
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Three water-soluble fluorophores are synthesized from 1,3,5-tris-(4′- iodophenyl)benzene. The compound with salicylate groups exhibits a selective fluorescent quenching by Cu2+via a static quenching mechanism. The addition of Triton X-100 impro
- Sirilaksanapong, Sakan,Sukwattanasinitt, Mongkol,Rashatasakhon, Paitoon
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supporting information; experimental part
p. 293 - 295
(2012/01/13)
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- New Trigonal Lattice Hosts: Stoicheiometric Crystal Inclusions of Laterally Trisubstituted Benzenes - X-Ray Crystal Structure of 1,3,5-Tris-(4-carboxyphenyl)benzene*Dimethylformamide
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New host molecules with a central 1,3,5-trisubstituted benzene ring and rigidly attached lateral arms composed of aryl or arylethynyl and extra fuctional groups are reported.They are shown to give more than thirty clathrates with a wide variety of organic solvents comprising alicyclic, aromatic, heterocyclic, dipolar aprotic, and protic molecules.Inclusion selectivities and stoicheiometries of the different clathrates are discussed.The crystal structure of (2a)*dimethylformamide (DMF) (1:3) inclusion compound has been determined from single-crystal X-ray diffraction.The crystals show R3 symmetry.There are six host and eighteen guest molecules in the hexagonal unit cell with a=b=23.160(9) and c=11.812(3) Angstroem.The final linear R is 0.082 for 1518 unique reflections.The host molecule adopts a propeller conformation with perfect three-fold symmetry and acts as a donor in hydrogen bonds to three DMF molecules.In the crystal structure the host-guest units are arranged stack-wise.
- Weber, Edwin,Hecker, Manfred,Koepp, Erich,Orlia, Wolfgang,Czugler, Matyas,Csoeregh, Ingeborg
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p. 1251 - 1258
(2007/10/02)
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