- Diazapentacenes from Quinacridones
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Bis(silylethynylated) 5,7- and 5,12-diazapentacenes were synthesized from cis- and trans-quinacridone using protection, alkynylation and deoxygenation. The solid-state packing of the targets is determined by choice and position of the silylethynyl substit
- Wiesner, Thomas,Ahrens, Lukas,Rominger, Frank,Freudenberg, Jan,Bunz, Uwe H. F.
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supporting information
p. 4553 - 4556
(2021/02/26)
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- Simultaneous Generation of a [2 × 2] Grid-Like Complex and a Linear Double Helicate: a Three-Level Self-Sorting Process
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Two constitutional dynamic libraries (CDLs) - each containing two amines, two dialdehydes, and two metal salts - have been found to self-sort, generating two pairs of imine-based metallosupramolecular architectures (sharing no component) each with a [2 ×
- Ayme, Jean-Fran?ois,Lehn, Jean-Marie,Bailly, Corinne,Karmazin, Lydia
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supporting information
p. 5819 - 5824
(2020/03/30)
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- Anion Recognition in Water by Charge-Neutral Halogen and Chalcogen Bonding Foldamer Receptors
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A novel strategy for the recognition of anions in water using charge-neutral σ-hole halogen and chalcogen bonding acyclic hosts is demonstrated for the first time. Exploiting the intrinsic hydrophobicity of halogen and chalcogen bond donor atoms integrated into a foldamer structural molecular framework containing hydrophilic functionalities, a series of water-soluble receptors was constructed for an anion recognition investigation. Isothermal titration calorimetry (ITC) binding studies with a range of anions revealed the receptors to display very strong and selective binding of large, weakly hydrated anions such as I- and ReO4-. This is achieved through the formation of 2:1 host-guest stoichiometric complex assemblies, resulting in an encapsulated anion stabilized by cooperative, multidentate, convergent σ-hole donors, as shown by molecular dynamics simulations carried out in water. Importantly, the combination of multiple σ-hole-anion interactions and hydrophobic collapse results in I- affinities in water that exceed all known σ-hole receptors, including cationic systems (β2 up to 1.68 × 1011 M-2). Furthermore, the anion binding affinities and selectivity trends of the first example of an all-chalcogen bonding anion receptor in pure water are compared with halogen bonding and hydrogen bonding receptor analogues. These results further advance and establish halogen and chalcogen bond donor functions as new tools for overcoming the challenging goal of anion recognition in pure water.
- Borissov, Arseni,Marques, Igor,Lim, Jason Y.C.,Félix, Vítor,Smith, Martin D.,Beer, Paul D.
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supporting information
p. 4119 - 4129
(2019/03/07)
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- A halogen-bonding foldamer molecular film for selective reagentless anion sensing in water
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We describe self-assembled monolayers of novel halogen-bonding and hydrogen-bonding foldamer receptors capable of selectively recruiting perrhenate, iodide and thiocyanate in water. Unprecedented anion sensing via impedance-derived capacitance spectroscopy enables subsequent sensitive and selective anion detection without the need for a redox probe. Importantly, the sensing of any anion should be possible using this novel electrochemical approach.
- Hein, Robert,Borissov, Arseni,Smith, Martin D.,Beer, Paul D.,Davis, Jason J.
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supporting information
p. 4849 - 4852
(2019/05/02)
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- Synthesis of a Helical Analogue of Kekulene: A Flexible ?€-Expanded Helicene with Large Helical Diameter Acting as a Soft Molecular Spring
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A π-expanded helicene that is the helically twisted analogue of kekulene was synthesized using a 6-fold ring-closing olefin metathesis (RCM) reaction as a key step. The π-expanded geometry with large helical diameter (dh = 10.2 ?), consisting o
- Nakakuki, Yusuke,Hirose, Takashi,Matsuda, Kenji
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supporting information
p. 15461 - 15469
(2018/11/23)
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- Versatile synthesis of tunable N,S-bridged-[1.1.1.1]-cyclophanes promoted by ester functions
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We report herein a powerful and highly adaptable metal-free organic synthetic route to functionalized N,S- bridged-[1.1.1.1]-cyclophanes using an ester-promoted macrocyclisation step. The newly synthesized cyclophanes are obtained in good yields exhibitin
- Malytskyi, Volodymyr,da Silva, Vinicius Demetrio,Siri, Olivier,Giorgi, Michel,Raimundo, Jean-Manuel
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p. 6363 - 6367
(2016/09/23)
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- NOVEL COMPOUNDS FOR ORGANIC ELECTRONIC MATERIAL AND ORGANIC ELECTRONIC DEVICE USING THE SAME
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PROBLEM TO BE SOLVED: To provide: novel compounds for organic electronic material which may be included in a hole transport layer, electron transport layer or hole injection layer or may be used as a host or dopant; and an organic electronic element using
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Paragraph 0051-0052
(2016/10/17)
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- V-shaped rigid bidentate carboxylic acid ligand, and preparation method and application thereof
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The invention relates to a V-shaped rigid bidentate carboxylic acid ligand, and a preparation method and an application thereof. A technical scheme adopted in the invention is characterized in that the structural formula of the V-shaped rigid bidentate ca
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Paragraph 0014; 0021
(2017/02/17)
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- Novel Compounds for Organic Electronic Material and Organic Electronic Device Using the Same
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The present invention relates to a novel compound for an organic electronic material and an organic electronic device containing the same. The compound for an organic electronic material according to the present invention is indicated as a chemical formul
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Paragraph 0099-0102
(2020/03/20)
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- Four- and Sixfold Tandem-Domino Reactions Leading to Dimeric Tetrasubstituted Alkenes Suitable as Molecular Switches
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A highly efficient palladium-catalyzed fourfold tandem-domino reaction consisting of two carbopalladation and two C-H-activation steps was developed for the synthesis of two types of tetrasubstituted alkenes 3 and 6 with intrinsic helical chirality starting from substrates 1 and 4, respectively. A sixfold tandem-domino reaction was also developed by including a Sonogashira reaction. 20 compounds with different substitution patterns were prepared with yields of up to 97%. Structure elucidation by X-ray crystallography confirmed helical chirality of the two alkene moieties. Photophysical investigations of some of the compounds showed pronounced switching properties through light-controlled changes of their stereochemical configuration.
- Tietze, Lutz F.,Waldecker, Bernd,Ganapathy, Dhandapani,Eichhorst, Christoph,Lenzer, Thomas,Oum, Kawon,Reichmann, Sven O.,Stalke, Dietmar
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supporting information
p. 10317 - 10323
(2015/09/01)
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- Versatile Tailoring of Paddle-Wheel ZnII Metal-Organic Frameworks through Single-Crystal-to-Single-Crystal Transformations
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A new tetracarboxylate ligand having short and long arms formed 2D layer ZnII coordination polymer 1 with paddle-wheel secondary building units under solvothermal conditions. The framework undergoes solvent-specific single crystal-to-single crystal (SC-SC) transmetalation to produce 1Cu. With a sterically encumbered dipyridyl linker, the same ligand forms non-interpenetrated, 3D, pillared-layer ZnII metal-organic framework (MOF) 2, which takes part in SC-SC linker-exchange reactions to produce three daughter frameworks. The parent MOF 2 shows preferential incorporation of the longest linker in competitive linker-exchange experiments. All the 3D MOFs undergo complete SC-SC transmetalation with CuII, whereby metal exchange in different solvents and monitoring of X-ray structures revealed that bulky solvated metal ions lead to ordering of the shortest linker in the framework, which confirms that the solvated metal ions enter through the pores along the linker axis.
- Pal, Tapan K.,Neogi, Subhadip,Bharadwaj, Parimal K.
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supporting information
p. 16083 - 16090
(2015/11/03)
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- Dinuclear iridium(III) complexes containing bibenzimidazole and their application to water photoreduction
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An efficient three-component catalytic system for visible-light-induced production of hydrogen from water was developed based on new dinuclear iridium photosensitizers (PSs), [Ir(tfdpyb)Cl]2(BiBzIm) (P1) and [Ir(tfmppy)2]2BiBzIm (P2) [tfdpyb = 1,3-di(2-pyridyl)-4,6- bis(trifluoromethyl)benzene, tfmppy = 2-(4-(trifluoromethyl)phenyl)-pyridine, BiBzIm = 2,2′-bibenzimidazole]. These iridium complexes were fully characterized by 1H NMR and ESI-MS, and their photophysical properties and electrochemical behaviors were also investigated. To compare with this new type of iridium compounds, the mononuclear analogues Ir(tfdpyb)(BiBzImH)Cl (P3), Ir(tfmppy)2(BiBzImH) (P4), and Ir(dpyx)(BiBzImH)Cl (P5) (dpyx = 1,3-di(2-pyridyl)-4,6-dimethylbenzene) were also synthesized. The absorption spectra of dinuclear and mononuclear complexes are similar mainly in terms of their shape in the visible-light region, but as expected, the dinuclear species are more intense (approximately twice) compared with the corresponding mononuclear compounds. These complexes were tested as PSs with regard to their capacity to reduce water in the photocatalytic system for hydrogen production together with a series of water reduction catalysts and triethanolamine (TEOA) as a sacrificial electron donor. Turnover numbers up to 3780 for the dinuclear iridium complex P1 and 1020 for the mononuclear iridium compound P3 were obtained under the identical conditions. The results indicate that dinuclear iridium compounds can behave as PSs to be used for reducing water to hydrogen, and their activity was superior to that of the mononuclear compounds in this system. This work provides us a more general architectural guideline for constructing metal complexes as light-harvesting materials for visible-light-induced hydrogen production.
- Cai, Jian-Guang,Yu, Zhen-Tao,Yuan, Yong-Jun,Li, Feng,Zou, Zhi-Gang
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p. 1953 - 1963
(2014/06/24)
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- Catalysts, processes for making catalysts, processes for making polyolefin compositions and polyolefin compositions
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The present invention relates to compositions and processes of making catalysts and polyolefins. More particularly, the invention relates to to snap shut catalysts, processes for making the catalysts, processes for making polyolefins using the catalysts and the polyolefins resulting therefrom.
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Page/Page column
(2014/08/06)
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- Catalysts, processes for making catalysts, processes for making polyolefin compositions, and polyolefin compositions
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The present invention relates to compositions and processes of making catalysts and polyolefins. More particularly, the invention relates to snap shut catalysts, processes for making the catalysts, processes for making polyolefins using the catalysts and
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- Highly active catalysts for the transfer dehydrogenation of alkanes: Synthesis and application of novel 7-6-7 ring-based pincer iridium complexes
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A series of Ir-PCP pincer precatalysts [(7-6-7-RPCP)Ir(H)(Cl)] and [(7-6-7-ArPCP)Ir(H)(Cl)(MeCN)] bearing a novel "7-6-7" fused-ring skeleton have been synthesized based upon the postulate that the catalytic species would have durability due to their rather rigid structure and high activity owing to the low but sufficient flexibility of their backbones, which are not completely fixed. Treatment of these precatalysts with NaOtBu gave rise to the active 14 electron (14e) species [(7-6-7-iPrPCP)Ir] and [(7-6-7-PhPCP)Ir], which can trap hydrogen and were spectroscopically characterized as the tetrahydride complexes. Both [(7-6-7-iPrPCP)Ir] and [(7-6-7-PhPCP)Ir] were found to be highly effective in the transfer dehydrogenation of cyclooctane with tert-butylethylene as the hydrogen acceptor, the initial reaction rate at high temperature (230°C) being higher for [(7-6-7-iPrPCP)Ir] than [(7-6-7-PhPCP)Ir], and the turnover number (TON) of the overall hydrogen transfer being higher for the latter. Nonetheless, the estimated TONs were as high as 4600 and 4820 for the two complexes at this temperature, respectively, which are unprecedented absolute values. In terms of durability, the [(7-6-7-PhPCP)Ir] complex is the catalyst of choice for this reaction. Structural analysis and computational studies support the importance of the low flexibility of the ligand core. Copyright
- Shi, Yuan,Suguri, Takuya,Dohi, Chisato,Yamada, Hirotsuna,Kojima, Satoshi,Yamamoto, Yohsuke
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supporting information
p. 10672 - 10689
(2013/08/23)
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- Luminescent iridium(III) complexes with N^C^N- coordinated terdentate ligands: Dual tuning of the emission energy and application to organic light-emitting devices
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A family of complexes (1a-3a and 1b-3b) was prepared, having the structure Ir(N^C^N)(N^C)Cl. Here, N^C ^N represents a terdentate, cyclometallating ligand derived from 1,3-di(2-pyridyl)benzene incorporating CH3 (1a,b), F (2a,b), or CF3 (3a,b) substituents at the 4 and 6 positions of the benzene ring, and N^C is 2-phenylpyridine (series a) or 2-(2,4-difluorophenyl) pyridine (series b). The complexes are formed using a stepwise procedure that relies on the initial introduction of the terdentate ligand to form a dichloro-bridged iridium dimer, followed by cleavage with the N^C ligand. 1H NMR spectroscopy reveals that the isomer that is exclusively formed in each case is that in which the pyridyl ring of the N ^C ligand is trans to the cyclometallating aryl ring of the N ^C^N ligand. This conclusion is unequivocally confirmed by X-ray diffraction analysis for two of the complexes (1b and 3a). All of the complexes are highly luminescent in degassed solution at room temperature, emitting in the green (1a,b), blue-green (2a,b), and orange-red (3a,b) regions. The bidentate ligand offers independent fine-tuning of the emission energy: for each pair, the "b" complex is blue-shifted relative to the analogous "a" complex. These trends in the excited-state energies are rationalized in terms of the relative magnitudes of the effects of the substituents on the highest occupied and lowest unoccupied orbitals, convincingly supported by time-dependent density functional theory (TD-DFT) calculations. Luminescence quantum yields are high, up to 0.7 in solution and close to unity in a PMMA matrix for the green-emitting complexes. Organic light emitting devices (OLEDs) employing this family of complexes as phosphorescent emitters have been prepared. They display high efficiencies, at least comparable, and in some cases superior, to similar devices using the well-known tris-bidentate complexes such as fac-Ir(ppy)3. The combination of terdentate and bidentate ligands is seen to offer a versatile approach to tuning of the photophysical properties of iridium-based emitters for such applications.
- Brulatti, Pierpaolo,Gildea, Richard J.,Howard, Judith A. K.,Fattori, Valeria,Cocchi, Massimo,Williams, J. A. Gareth
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experimental part
p. 3813 - 3826
(2012/04/23)
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- CATALYSTS, PROCESSES FOR MAKING CATALYSTS, PROCESSES FOR MAKING POLYOLEFIN COMPOSITIONS, AND POLYOLEFIN COMPOSITIONS
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The present invention relates to compositions and processes of making catalysts and polyolefins. More particularly, the invention relates to snap shut catalysts, processes for making the catalysts, processes for making polyolefins using the catalysts and the polyolefins resulting therefrom.
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- METAL COMPLEX COMPOUND AND ORGANIC ELECTROLUMINESCENT DEVICE USING SAME
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A metal-complex compound which comprises a tridentate chelate ligand having a specified partial structure. An organic electroluminescence device which comprises at least one organic thin film layer sandwiched between a pair of electrode consisting of an anode and a cathode, wherein the organic thin film layer comprises the metal-complex compound, which emits light by applying an electric voltage between the pair of electrode. The present invention provides an organic EL device which emits blue light with high purity and of short wavelength with an enhanced efficiency of light emission.
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Page/Page column 32; 33
(2010/11/28)
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- Polycyclic aromatic hydrocarbons by ring-closing metathesis
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A strategy for the synthesis of polycyclic aromatic hydrocarbons (PAHs) by the ring-closing olefin metathesis (RCM) of pendant olefins on a phenylene backbone has been developed. RCM of 2,4′,6′,2″-tetravinyl-[1, 1′;3′,1″]terphenyl and 2,2′,5′,2″- tetravinyl-[1,1′;4′,1′]terphenyl affords in high yield the isomeric [a,j] and [a,h] dibenzanthracenes, respectively. In contrast with other intramolecular annulation methods, such as Friedel-Crafts acylations, this reaction is completely regioselective. Since RCM is reversible and PAHs are often thermodynamic sinks, this strategy is an effective and general method for the preparation of PAHs. Density functional theory calculations support these results. Carbon disulfide is a suitable solvent for these reactions.
- Bonifacio, Margel C.,Robertson, Charles R.,Jung, Jun-Young,King, Benjamin T.
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p. 8522 - 8526
(2007/10/03)
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- The synthesis of singlet ground state derivatives of non-Kekule polynuclear aromatics
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It is known that a two-electron reduction of tetrabutylammonium 3,4-dioxo-4H,8H-dibenzo[cd,mn]pyren12-olate gives a trioxy (tri-O-) derivative of the non-Kekule polynuclear aromatic compound dibenzo[cd,mn]pyrene (triangulene). This derivative is stable in solution and, like triangulene itself, has a triplet ground state. In exploring the generality of this strategy for the synthesis of high-spin derivatives of non-Kekule polynuclear aromatic compounds we have investigated two electron reductions of 4,8-dioxo-4H,8H-dibenzo[cd,mn]pyrene (to give a dioxy derivative of triangulene), 7,8-dioxo-7H,8H-dibenzo[de,hi]naphthacene (to give a dioxy derivative of dibenzo[de,hi]naphthacene) and 7,9-dioxo-7H,9H-dibenzo[de,jk]pentacene (to give a dioxy derivative of dibenzo[de,jk]pentacene). Dibenzo-[cd,mn]pyrene (triangulene), dibenzo[de,hi]naphthacene and dibenzo[de,jk]pentacene should all have triplet ground states, but the presence of two O- substituents on these aromatic nuclei will (just) lift the degeneracy of the putative singly occupied molecular orbitals. We have shown that the splitting this produces is sufficient to ensure that all of these dioxy derivatives have singlet ground states. Hence the strategy employed for making and stabilising triplet triangulene as its trioxy derivative does not provide a paradigm for other high-spin non-Kekule polynuclear aromatics. The reduction reactions were studied by cyclic voltammetry, by UV-VIS spectroscopy, and by EPR spectroscopy. Improved synthetic routes are described for 7,8-dioxo-7H,8H-dibenzo[de,hi]naphthacene and for 7,9-dioxo-7H,9H-dibenzo[de,jk]-pentacene. Violent explosions were encountered in attempts to repeat the literature procedure for the synthesis of 4,6-dichlorobenzene-1,3-dicarboxylic acid.
- Allinson, Graeme,Bushby, Richard J.,Jesudason, Malini V.,Paillaud, Jean-Louis,Taylor, Norman
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p. 147 - 156
(2007/10/03)
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- A simple and improved procedure for selective ring bromination of alkyl-substituted aromatic hydrocarbons on the surface of alumina
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Highly selective ring bromination of alkyl-substituted aromatic hydrocarbons has been achieved using molecular bromine adsorbed on the surface of alumina without any solvent.
- Ranu,Sarkar,Chakraborty
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p. 1095 - 1099
(2007/10/02)
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