- Tuning of electronic properties via labile N→B-coordination in conjugated organoboranes
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In this report we demonstrate that labile intramolecular N→B-Lewis pair formation can serve to tailor the properties of π-conjugated electronic materials. A series of boranes has been prepared by copper-catalyzed 1,3-dipolar azide-alkyne ‘click’-cycloaddi
- Schraff, Sandra,Sun, Yu,Pammer, Frank
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Read Online
- Linear and Radial Conjugation in Extended π-Electron Systems
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We describe the synthesis and electronic properties of new π-conjugated small molecules and polymers that combine the linear intramolecular conjugation pathways commonly associated with organic electronic materials with the emerging properties of radial c
- Peters, Garvin M.,Grover, Girishma,Maust, Ruth L.,Colwell, Curtis E.,Bates, Haley,Edgell, William A.,Jasti, Ramesh,Kertesz, Miklos,Tovar, John D.
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Read Online
- Dibenzoanthradiquinone Building Blocks for the Synthesis of Nitrogenated Polycyclic Aromatic Hydrocarbons
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A straightforward method for the synthesis of two dibenzo[a,h]anthracene-5,6,12,13-diquinone building blocks is reported. To showcase their usefulness, a series of dibenzo[a,h]anthracene nitrogenated derivatives have been synthesized that show different optoelectronic, redox, and charge transport properties, illustrating their potential as organic semiconductors.
- Martínez, Jose I.,Mora-Fuentes, Juan P.,Carini, Marco,Saeki, Akinori,Saeki, Akinori,Melle-Franco, Manuel,Mateo-Alonso, Aurelio,Mateo-Alonso, Aurelio
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Read Online
- Flexible side arms of ditopic linker as effective tools to boost proton conductivity of Ni8-pyrazolate metal-organic framework
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Two primitive metal-organic frameworks (MOFs), NiL1 and NiL2, based on Ni8O6-cluster and ditopic pyrazolate linkers, L1 (with rigid alkyne arms) and L2 (with flexible alkyne chains), were prepared. The proton conductivities of these MOFs in pristine form and imidazole-encapsulated forms, Im@NiL1 and Im@NiL2, were measured and compared. Upon introduction of imidazole molecules, the proton conductivity could be increased by 3 to 5 orders of magnitude and reached as high as 1.72 × 10?2 S/cm (at 98% RH and 80 °C). Also, whether imidazole molecules were introduced or not, Ni8O6-based MOFs with L2 in general gave better proton conductivity than those with L1 signifying that flexible side arms indeed assist proton conduction probably via establishment of efficient proton-conducting channels along with formation of highly ordered domains of water/imidazole molecules within the network cavities. Beyond the active Ni8O6-cluster, tuning flexibility of linker pendants serves as an alternative approach to regulate/modulate the proton conductivity of MOFs.
- Chung, Lai-Hon,Feng, Zihao,He, Jun,Hu, Jieying,Li, Jian-Rong,Liao, Wei-Ming,Luo, Qian-Ru,Wu, Can-Min,Zhang, Hu,Zhong, Yuan-Hui
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- Linker Deficiency, Aromatic Ring Fusion, and Electrocatalysis in a Porous Ni8-Pyrazolate Network
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The cruciform linker molecule here features two designer functions: the pyrazole donors for framework construction, and the vicinal alkynyl units for benzannulation to form nanographene units into the Ni8-pyrazolate scaffold. Unlike the full 12 connections of the Ni8(OH)4(H2O)2 clusters in other Ni8-pyrazolate networks, significant linker deficiency was observed here, leaving about half of the Ni(II) sites capped by acetate ligands, which can be potentially removed to open the metal sites for reactivity. The crystalline Ni8-pyrazolate scaffold also retains the crystalline order even after thermal treatments (up to 300 °C) that served to partially graphitize the neighboring alkyne units. The resultant nanographene components enhance the electroactive properties of the porous hosts, achieving hydrogen evolution reaction (HER) activity that rivals that of topical nickel/palladium-enabled materials.
- Hu, Jieying,Deng, Xiangling,Zhang, Hu,Diao, Yingxue,Cheng, Shengxian,Zheng, Sai-Li,Liao, Wei-Ming,He, Jun,Xu, Zhengtao
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p. 161 - 166
(2021/01/11)
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- The kinetics and mechanism of interconversion within a system of [Fe2L 3]4+helicates and [Fe4L 6]8+cages
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Nature builds simple molecules into highly complex assemblies, which are involved in all fundamental processes of life. Some of the most intriguing biological assemblies are those that can be precisely reconfigured to achieve different functions using the same building blocks. Understanding the reconfiguration of synthetic self-assembled systems will allow us to better understand the complexity of proteins and design useful artificial chemical systems. Here we have prepared a relatively simple system in which two distinct self-assembled structures, a [Fe2L3]4+ helicate and a [Fe4L6]8+ cage that are formed from the same precursors, coexist at equilibrium. We have measured the rates of interconversion of these two species and propose a mechanism for the transformation.
- Al-Fayaad, Hydar A.,Arachchige, Kasun S. A.,Brock, Aidan J.,Clegg, Jack K.,Luis, Ena T.,McMurtrie, John C.,Micallef, Aaron S.,Siddique, Rashid G.,Thoburn, John D.
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p. 4918 - 4921
(2021/05/26)
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- B/N-Doped p-Arylenevinylene Chromophores: Synthesis, Properties, and Microcrystal Electron Crystallographic Study
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Linearly conjugated systems have long served as an archetype of conjugated materials, but suffer from two intrinsic structural problems: potential instability due to intermolecular interactions and the flexibility of the C-C bonds connecting C═C bonds. Ef
- Lu, Hua,Nakamuro, Takayuki,Yamashita, Keitaro,Yanagisawa, Haruaki,Nureki, Osamu,Kikkawa, Masahide,Gao, Han,Tian, Jiangwei,Shang, Rui,Nakamura, Eiichi
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p. 18990 - 18996
(2020/11/13)
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- Organic electroluminescence compound with diphosphopentadiene condensed ring and synthesis method of compound
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The invention discloses an organic electroluminescence compound with a diphosphopentadiene condensed ring and a synthesis method of the compound, and belongs to organophosphorus electroluminescence materials. The compound has a structure general formula as shown in a formula (I), wherein E is O or S, and a pi-conjugated group is phenyl or thiophene and the like. The compound can serve as a luminescent layer of an organic electroluminescence device to be applied to electroluminescence devices, luminescence properties of the device can be effectively changed by simply and chemically modifying phosphorus atoms and changing the pi-conjugated group, adjustment and control from blue light to yellow light are achieved, the compound is good in heat stability, natures of cis-trans-isomer devices are almost indistinguishable, the cis-trans-isomer devices has excellent charge injection and transmitting capacity, and the efficiency and the service lives of the corresponding organic electroluminescence devices can be remarkably improved.
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Paragraph 0026; 0027; 0028; 0029
(2018/10/19)
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- Illuminating tetra-ligand trapezoid organic boron compound, and preparation method and application thereof
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The invention discloses an illuminating tetra-ligand trapezoid organic boron compound, and a preparation method and an application thereof. The structural formula is shown in the specification, wherein the structure of R is shown in the specification and
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Paragraph 0046-0048
(2017/05/02)
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- Fluoride binding to an organoboron wire controls photoinduced electron transfer
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We demonstrate that the rates for long-range electron transfer can be controlled actively by tight anion binding to a rigid rod-like molecular bridge. Electron transfer from a triarylamine donor to a photoexcited Ru(bpy)32+ acceptor (bpy = 2,2′-bipyridine) across a 2,5-diboryl-1,4-phenylene bridge occurs within less than 10 ns in CH2Cl2 at 22 °C. Fluoride anions bind with high affinity to the organoboron bridge due to strong Lewis base/Lewis acid interactions, and this alters the electronic structure of the bridge drastically. Consequently, a large tunneling barrier is imposed on photoinduced electron transfer from the triarylamine to the Ru(bpy)32+ complex and hence this process occurs more than two orders of magnitude more slowly, despite the fact that its driving force is essentially unaffected by fluoride addition. Electron transfer rates in proteins could potentially be regulated via a similar fundamental principle, because interactions between charged amino acid side chains and counter-ions can modulate electronic couplings between distant redox partners. In artificial donor-bridge-acceptor compounds, external stimuli have been employed frequently to control electron transfer rates, but the approach of exploiting strong Lewis acid/Lewis base interactions to regulate the tunneling barrier height imposed by a rigid rod-like molecular bridge is conceptually novel and broadly applicable, because it is largely independent of the donor and the acceptor, and because the effect is not based on a change of the driving-force for electron transfer. The principle demonstrated here can potentially be used to switch between conducting and insulating states of molecular wires between electrodes. This journal is
- Chen, Jing,Wenger, Oliver S.
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p. 3582 - 3592
(2015/05/27)
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- CONJUGATED POLYMERS
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The invention relates to novel conjugated polymers containing one or more repeating units derived from indacenodibenzothiophene or dithia-dicyclopenta-dibenzothiophene, to methods for their preparation and educts or intermediates used therein, to polymer blends, mixtures and formulations containing them, to the use of the polymers, polymer blends, mixtures and formulations as organic semiconductors in organic electronic (OE) devices, especially in organic photovoltaic (OPV) devices, and to OE and OPV devices comprising these polymers, polymer blends, mixtures or formulations.
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Paragraph 0400-0402
(2017/02/23)
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- Multigram synthesis of bis[(trimethylsilyl)ethynyl]benzenes suitable for post-polymerization modification
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Novel substituted bis[(trimethylsilyl)ethynyl]benzenes have been prepared as versatile building blocks for organic functional materials. The resulting effects of replacing sulfur by selenium and tellurium on photophysical and electrochemical properties ha
- Gl?cklhofer, Florian,Lumpi, Daniel,St?ger, Berthold,Fr?hlich, Johannes
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supporting information
p. 2229 - 2232
(2014/06/09)
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- GRAPHENE NANORIBBONS, METHODS OF MAKING SAME, AND USES THEREOF
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Provided are graphene nanoribbons (GNRs), methods of making GNRs, and uses of the GNRs. The methods can provide control over GNR parameters such as, for example, length, width, and edge composition (e.g., edge functional groups). The methods are based on a metal catalyzed cycloaddition reaction at the carbon-carbon triple bonds of a poly(phenylene ethynylene) polymer. The GNRs can be used in devices such a microelectronic devices.
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Paragraph 0068; 0069
(2014/08/07)
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- Synthesis and characterization of a low-bandgap poly(arylene ethynylene) having donor-acceptor type chromophores in the side chain
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A low-bandgap poly(arylene ethynylene) (PAE) having donor-acceptor type chromophores in the side chain was synthesized. A π-conjugated PAE precursor having electron-rich dioctylanilino-substituted alkynes in the side chain was polymerized through Sonogashira cross-coupling reaction between functional monomers M-I with terminal acetylenes and M-II with diiodide, using tetrakis(tripheneylphosphine)palladium and copper iodide catalysts in a mixed solvent of triethylamine and tetrahydrofuran (THF) at 50°C. The electronically rich N,N-dioctylamino groups in M-I activated the alkynes in the side chains of M-I, thus making the selective reaction of sidechain alkynes with TCNE possible in the post-functionalization step. The selective reaction of TCNE (tetracyanoethylene) with activated dioctylanilino substituted alkynes in the side chains of precursor polymer afforded the target poly(arylene ethynylene). This unique polymer shows enhanced thermal stability and exhibits strong intramolecular charge-transfer interactions, resulting in a very low bandgap of poly(arylene ethynylene).
- Huang, Wenyi,Chen, Hongyan
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p. 2032 - 2037
(2013/04/24)
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- Highly efficient benzannulation of poly(phenylene ethynylene)s
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Put a ring on it: Sterically congested polyarylenes can be synthesized by benzannulation reactions at each C≡C bond of a poly(phenylene ethynylene) (see picture), one of the most easily synthesized and versatile classes of conjugated polymers. The benzannulation reaction is highly specific and efficient, as determined by an isotopic labeling study and several complementary spectroscopic methods. Copyright
- Arslan, Hasan,Saathoff, Jonathan D.,Bunck, David N.,Clancy, Paulette,Dichtel, William R.
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p. 12051 - 12054
(2013/01/16)
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- One-step synthesis of ladder-type fused poly(benzopentalene) derivatives with tunable energy levels by variable substituents
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Novel ladder-type conjugated polymers, fused poly (benzopentalene) derivatives, were synthesized from the readily accessible 1,4-dibromo-2,5- diethynylbenzene derivatives by the Pd-catalyzed self-polycondensation in one-step with high yields. The low solu
- Wang, Dong,Michinobu, Tsuyoshi
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scheme or table
p. 72 - 81
(2011/10/08)
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- Regiocontrolled synthesis of ethene-bridged para-phenylene oligomers based on PtII- And RuII-catalyzed aromatization
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We report the regiocontrolled syntheses of ethene-bridged paraphenylene oligomers in three distinct classes by using PtII- and Ru II-catalyzed aromatization. This synthetic approach has been developed based on twofold aromatization of the 1-aryl-2-alkynylbenzene functionality, which proceeds by distinct regioselectivity for platinum and ruthenium catalysts. Variable-temperature NMR spectra provide evi-dence that large arrays of these oligomers are prone to twist from planarity. The UV/Vis and photoluminescence (PL) spectra as well as the band gaps of these regularly growing arrays show a pattern of extensive π conjugation with increasing array sizes, except for in one instance.
- Chen, Tse-An,Lee, Te-Ju,Lin, Ming-Yuan,Sohel, Shariar M. A.,Diau, Eric Wei-Guang,Lush, Shie-Fu,Liu, Rai-Shung
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supporting information; experimental part
p. 1826 - 1833
(2010/06/19)
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- Benzodichalcogenophenes with Perfluoroarene Termini
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(Chemical Equation Presented) Benzodichalcogenophenes are functionalized at their termini via SNAr reactions of their bismetalates with perfluoroarenes. The identities of X, Y, and W are varied to study the effects on LUMO energy levels and cry
- Wang, Yongfeng,Parkin, Sean R.,Watson, Mark D.
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supporting information; experimental part
p. 4421 - 4424
(2009/05/11)
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- Facile synthesis, structure, and properties of benzo[1,2-b:4,5-b′] dichalcogenophenes
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A general and convenient synthesis of benzo[1,2-b:4,5-b′]- dichalcogenophenes including the thiophene (BDT, 1), selenophene (BDS, 2), and tellurophene (BDTe, 3) homologues is developed. Thus synthesized heterocycles are structurally characterized by single-crystal X-ray analysis, and all three homologues are isostructural with one another. They all have completely planar molecular structures packed in a herringbone arrangement. Their physicochemical properties were also elucidated by means of cyclic voltammetry (CV) and UV-vis spectra.
- Takimiya, Kazuo,Konda, Yasushi,Ebata, Hideaki,Niihara, Naoto,Otsubo, Tetsuo
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p. 10569 - 10571
(2007/10/03)
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- Structure-property relationships of donor/acceptor-functionalized tetrakis(phenylethynyl)benzenes and bis(dehydrobenzoannuleno)benzenes
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A series of tetrakis(phenylethynyl)benzenes and bis(dehydrobenzoannuleno) benzenes have been synthesized containing tetra-substitutions of neutral, donor, and mixed donor/acceptor groups. To ascertain the importance of substitutional and structural differ
- Marsden, Jeremiah A.,Miller, Jeremie J.,Shirtcliff, Laura D.,Haley, Michael M.
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p. 2464 - 2476
(2007/10/03)
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- Short and efficient synthesis of coronene derivatives via ruthenium-catalyzed benzannulation protocol
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TpRuPPh3(CH3CN)2PF6 (3 mol %) was very active in catalytic benzannulation of 1-phenyl-2-ethynylbenzenes in dichloroethane (60 °C, 36 h) to afford phenanthrene in 95% yield. This method is applicable to the synthesis of various polycyclic aromatic hydrocarbons via two- and four-fold benzannulations, including various substituted coronene derivatives (53-86% yields) using this catalyst at a moderate loading (10 mol %).
- Shen, Hung-Chin,Tang, Jhih-Meng,Chang, Hsu-Kai,Yang, Chia-Wei,Liu, Rai-Shung
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p. 10113 - 10116
(2007/10/03)
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- Synthesis and Optical Properties of Donor-Acceptor Tetrakis(phenyl-ethynyl) benzenes
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A simple and efficient synthesis of a series of donor-acceptor substituted 1,2,4,5-tetrakis(phenylethynyl)benzenes is described. The molecules constructed exhibit interesting optical properties. Preliminary studies show that the tetraynes hold promise as
- Miller, Jeremie J.,Marsden, Jeremiah A.,Haley, Michael M.
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p. 165 - 168
(2007/10/03)
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- Exploiting the versatility of organometallic cross-coupling reactions for entry into extended aromatic systems
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Using a variety of Pd-catalyzed cross-coupling techniques, we have prepared several pendant arene derivatives (5,6,12,15). From these materials, we have expanded upon earlier work and developed new electrophilic cyclization strategies. By employing suffic
- Tovar, John D,Swager, Timothy M
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p. 215 - 222
(2007/10/03)
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