- Pyrazine-based donor tectons: Synthesis, self-assembly and characterization
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Two new supramolecular building blocks derived from pyrazine are introduced. These molecules, having pendant pyridine units covalently linked to central pyrazine ring, are structurally rigid with pre-defined bite angles. Therefore they can act as donor tectons in design of supramolecular hexagons using coordination driven self-assembly protocol. Multinuclear NMR (including 1H DOSY) and mass spectrometry have been utilized to confirm the purity and stoichiometry of these self assembled hexagonal ensembles. PM6 molecular modeling studies corroborate their hexagonal shape and nanoscalar dimensions.
- Bhowmick, Sourav,Chakraborty, Sourav,Marri, Subba R.,Behera,Das, Neeladri
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- A Triazine-Based Analogue of Graphyne: Scalable Synthesis and Applications in Photocatalytic Dye Degradation and Bacterial Inactivation
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Graphyne, a theorized carbon allotrope possessing only sp- and sp2-hybridized carbon atoms, holds great potentials in many fields, especially in catalysis and energy-transfer/storage devices. Using a bottom-up strategy, we synthesized a new N-doped graphyne analogue, triazine- and 1,4-diethynylbenzene-based graphyne TA-BGY, in solution in gram-scale. The unique sp/sp2 carbon-conjugated TA-BGY possesses an extended porous network structure with a BET surface area of approximately 300 m2 g?1. Owing to its low optical band gap (1.44 eV), TA-BGY was expected to have many applications, which were exemplified by the photodegradation of methyl orange and photocatalytic bacterial inactivation.
- Chen, Tao,Li, Wen-Qian,Chen, Xiao-Jia,Guo, Yun-Zhe,Hu, Wei-Bo,Hu, Wen-Jing,Liu, Yahu A.,Yang, Hui,Wen, Ke
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- Study on synthesis, characterization, and nonvolatile memory behavior of ferrocene-containing metallopolymers
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In this work, two metallopolymers (P1 and P2)were designed and synthesized through coupling of ferrocene-anchored fluorene derivatives with porphyrin and benzene based diethynyl ligand, respectively. The chemical structure and physical properties of these two metallpolymers were fully characterized, which indicate that these two metallopolymers are thermally stable and semiconducting. Then, sandwich-like organic resistive memory based on P1 and P2 for data storage were explored. The memory device testing results manifest that both P1 and P2 are of the stable electric bistability and show write once read many times memory (WORM)characteristics.
- Cheng, Xiaozhe,Md, Asaduzzaman,Lian, Hong,Zhong, Zheng,Guo, Hongen,Dong, Qingchen,Roy
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- Structurally-Defined, Sulfo-Phenylated, Oligophenylenes and Polyphenylenes
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We report the synthesis and molecular characterization of structurally defined, sulfo-phenylated, oligo- and polyphenylenes that incorporate a novel tetra-sulfonic acid bistetracyclone monomer. The utility of this monomer in the [4 + 2] Diels-Alder cycloaddition to produce well-defined, sulfonated oligophenylenes and pre-functionalized polyphenylene homopolymers is demonstrated. Characterization of the oligophenylenes indicates formation of the meta-meta and para-para adducts in a ～ 1:1 ratio. These functionalized monomers and their subsequent coupling provide a route to prepare novel, sterically encumbered, sulfonated polyphenylenes possessing unprecedented structural control.
- Skalski, Thomas J. G.,Britton, Benjamin,Peckham, Timothy J.,Holdcroft, Steven
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- Fluorescence and visual sensing of nitroaromatic explosives using electron rich discrete fluorophores
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Several π-electron rich fluorescent aromatic compounds containing trimethylsilylethynyl functionality have been synthesized by employing Sonogashira coupling reaction and they were characterized fully by NMR ( 1H, 13C)/IR spectroscop
- Shanmugaraju, Sankarasekaran,Joshi, Sachin A.,Mukherjee, Partha Sarathi
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- C-Au Covalently Bonded Molecular Junctions Using Nonprotected Alkynyl Anchoring Groups
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We report on an approach to realize carbon-gold (C-Au) bonded molecular junctions without the need for an additive to deprotect the alkynyl carbon as endstanding anchor group. Using the mechanically controlled break junction (MCBJ) technique, we determine the most probable conductance value of a family of alkynyl terminated oligophenylenes (OPA(n)) connected to gold electrodes through such an akynyl moiety in ambient conditions. The molecules bind to the gold leads through an sp-hybridized carbon atom at each side. Comparing our results with other families of molecules that present organometallic C-Au bonds, we conclude that the conductance of molecules contacted via an sp-hybridized carbon atom is lower than the ones using sp3 hybridization due to strong differences in the coupling of the conducting orbitals with the gold leads.
- Olavarria-Contreras, Ignacio José,Perrin, Mickael L.,Chen, Zhi,Klyatskaya, Svetlana,Ruben, Mario,Van Der Zant, Herre S. J.
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- Arene-Inserted Extended Germa[n]pericyclynes: Synthesis, Structure, and Phosphorescence Properties
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This report describes the synthesis and characterization of arene-inserted extended (ArEx) germa[n]pericyclynes composed of germanium and 1,4-diethynylbenzene units. These novel cyclic germanium-π unit materials were synthesized with diethynylbenzene and germanium dichloride. X-ray crystallographic analysis revealed their structures, and the planar conformation of ArEx germa[4]pericyclyne along with the regular aromatic rings. UV/Vis absorption spectra and fluorescence emission spectra showed considerably unique and highly improved character compared to previously reported germa[n]pericyclynes. Even in the absence of transition metal components, phosphorescence emissions were observed, and the emission lifetimes were dramatically improved. ArEx germa[n]pericyclynes showed high photoluminescence quantum yields, whereas low photoluminescence quantum yields were observed for acyclic compounds. Density functional theory calculations show delocalized orbitals between skipped alkyne units through a germanium tether, and an increase in the HOMO energy level, leading to a small HOMO–LUMO energy gap.
- Tanimoto, Hiroki,Mori, Junta,Ito, Shunichiro,Nishiyama, Yasuhiro,Morimoto, Tsumoru,Tanaka, Kazuo,Chujo, Yoshiki,Kakiuchi, Kiyomi
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- Synthesis of Rigid Rod, Trigonal, and Tetrahedral Nucleobase-Terminated Molecules
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An efficient fragment splicing method for the construction of multiple nucleobase-terminated monomers has been developed. Conformationally fixed rod, trigonal planar and tetrahedral thymine and adenine structures were generated in moderate to good yields,
- Cheng, Liang,Jin, Xiao-Yang,Liu, An-Di,Liu, Li,Wu, Chuan-Shuo
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- Catalytic Decarboxylation of Silyl Alkynoates to Alkynylsilanes
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Herein, we describe a decarboxylative approach to the preparation of alkynylsilanes. Treatment of a silyl alkynoate in N,N-dimethylformamide (DMF) at 80 °C in the presence of catalytic amounts of CuCl and PCy3 produced the corresponding alkynylsilane in excellent yield. The copper-catalyzed decarboxylation proceeded smoothly with low catalyst loadings (0.5 mol % of CuCl and 1.0 mol % of PCy3) under mild reaction conditions and is easily scalable to gram quantities.
- Aoyagi, Keiya,Choi, Jun-Chul,Kawatsu, Takahiro,Matsumoto, Kazuhiro,Nakajima, Yumiko,Sato, Kazuhiko
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supporting information
(2020/09/15)
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- Microwave-assisted unprotected Sonogashira reaction in water for the synthesis of polysubstituted aromatic acetylene compounds
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A microwave-assisted, efficient and rapid Sonogashira reaction was developed for the synthesis of polysubstituted aromatic alkynes. The reaction was made environmentally friendly and easy to perform by replacing the traditional amine solvents with water.
- Tian, Yucheng,Wang, Jubo,Cheng, Xinying,Liu, Kang,Wu, Tizhi,Qiu, Xiaqiu,Kuang, Zijian,Li, Zhiyu,Bian, Jinlei
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supporting information
p. 1338 - 1344
(2020/03/11)
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- 2D arrays of organic qubit candidates embedded into a pillared-paddlewheel metal-organic framework
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The creation of ordered arrays of qubits that can be interfaced from the macroscopic world is an essential challenge for the development of quantum information science (QIS) currently being explored by chemists and physicists. Recently, porous metal?organic frameworks (MOFs) have arisen as a promising solution to this challenge as they allow for atomic-level spatial control of the molecular subunits that comprise their structures. To date, no organic qubit candidates have been installed in MOFs despite their structural variability and promise for creating systems with adjustable properties. With this in mind, we report the development of a pillared-paddlewheel-type MOF structure that contains 4,7-bis(2-(4-pyridyl)-ethynyl) isoindoline N-oxide and 1,4-bis(2-(4-pyridyl)-ethynyl)-benzene pillars that connect 2D sheets of 9,10-dicarboxytriptycene struts and Zn2(CO2)4 secondary binding units. The design allows for the formation of ordered arrays of reorienting isoindoline nitroxide spin centers with variable concentrations through the use of mixed crystals containing the secondary 1,4-phenylene pillar. While solvent removal causes decomposition of the MOF, magnetometry measurements of the MOF containing only N-oxide pillars demonstrated magnetic interactions with changes in magnetic moment as a function of temperature between 150 and 5 K. Variable-temperature electron paramagnetic resonance (EPR) experiments show that the nitroxides couple to one another at distances as long as 2 nm, but act independently at distances of 10 nm or more. We also use a specially designed resonance microwave cavity to measure the face-dependent EPR spectra of the crystal, demonstrating that it has anisotropic interactions with impingent electromagnetic radiation.
- Forbes, Malcolm D. E.,Garcia-Garibay, Miguel A.,Jellen, Marcus J.,Ayodele, Mayokun J.,Cantu, Annabelle
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supporting information
p. 18513 - 18521
(2020/11/27)
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- Mixed-Valent Molecular Triple Deckers
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Two phenothiazine (PTZ) moieties were connected via naphthalene spacers to a central arene to result in stacked PTZ-arene-PTZ structure elements. Benzene and tetramethoxybenzene units served as central arenes mediating electronic communication between the two PTZ units. Based on cyclic voltammetry, UV/Vis-NIR absorption, EPR spectroscopy, and computational studies, the one-electron oxidized forms of the resulting compounds behave as class II organic mixed-valence species in which the unpaired electron is partially delocalized over both PTZ units. The barrier for intramolecular electron transfer depends on the nature of the central arene sandwiched between the two PTZ moieties. These are the first examples of rigid organic mixed-valent triple-decker compounds with possible electron-transfer pathways directly across a stacked structure, and they illustrate the potential of oligo-naphthalene building blocks for long-range electron transfer and a future molecular electronics technology.
- Schmidt, Hauke C.,Guo, Xingwei,Richard, Pascal U.,Neuburger, Markus,Palivan, Cornelia G.,Wenger, Oliver S.
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supporting information
p. 11688 - 11691
(2018/09/10)
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- Organic electroluminescent element and preparation method of triazole derivative
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The invention discloses an organic electroluminescent element and a preparation method of a triazole derivative shown by the formula (I) as shown in the description. The organic electroluminescent element comprises an anode layer and a cathode layer which
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Paragraph 0106; 0107; 0108
(2018/10/11)
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- Catalytic Activation of Trimethylsilylacetylenes: A One-Pot Route to Unsymmetrical Acetylenes and Heterocycles
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For the synthesis of unsymmetrical acetylenes, a Sonogashira coupling-deprotection-Sonogashira coupling reaction sequence is often used. Removal of protecting groups requires harsh conditions or an excess of difficult to handle and expensive reagents. Herein, we disclose a novel catalytic method for the selective deprotection of trimethylsilylacetylenes in Sonogashira reaction. The reagent hexafluorosilicic acid, an inexpensive nontoxic compound, was used to promote the selective desilylation. This method enables the efficient synthesis of unsymmetric acetylenes with other silylated functional groups present. Further possibilities of the method were explored by synthesis of heterocycles.
- Lasányi, Dániel,Mészáros, ádám,Novák, Zoltán,Tolnai, Gergely L.
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p. 8281 - 8291
(2018/06/11)
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- Fluoroform-Derived CuCF3 for Trifluoromethylation of Terminal and TMS-Protected Alkynes
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An efficient trifluoromethylation reaction of alkynes using a fluoroform-derived CuCF3 reagent is described. The CF3 source is the inexpensive industrial waste fluoroform (CF3H). The air-stable CuCF3 reagent can be prepared in large quantities and is convenient to use. Synthetically useful trifluoromethylated alkynes containing a wide range of functional groups were successfully synthesized under mild conditions. Both terminal and TMS-protected alkynes gave the products in one step. The beneficial effect of a diamine ligand tetramethylethylenediamine (TMEDA) with the fluoroform-derived CuCF3 reagent was also demonstrated.
- He, Lisi,Tsui, Gavin Chit
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supporting information
p. 2800 - 2803
(2016/07/06)
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- Palladium catalyzed reactions executed on solid-phase peptide synthesis supports for the production of self-assembling peptides embedded with complex organic electronic subunits
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Methods to synthesize self-assembling peptides embedded with complex organic electronic subunits are provided.
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- Fast pirouetting motion in a pyridine bisamine-containing copper-complexed rotaxane
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The present work reports the introduction of pyridine bisamine terdentate ligands in the structure of a pirouetting copper rotaxane. Rotaxane 2[PF 6] constitutes the first example of the incorporation of imine-based dynamic covalent chemistry in the synthesis of switchable copper-complexed interlocked systems. In this rotaxane, the substitution of the classical terpyridine terdentate unit by a pyridine bisamine moiety has led to a significant stabilization of the pentacoordinated site. That fact has been evidenced by EPR spectroscopy and cyclic voltammetry. Regarding the tetracoordinated site, the congestion around the coordination sphere has been reduced to accelerate the typically slow reorganization of the CuII. Ethynyl-3,8-substitution on the axis phenanthroline along with the 2,9-diphenyl-1,10-phenanthroline (dpp) present in the macrocycle afforded a very stable coordination environment for CuI, which is at the same time labile upon oxidation. In summary, the incorporation of a pyridine bisamine unit as a terdentate ligand and the optimization of the bidentate ligand of the axle not only has led to a simplification of the synthetic procedures, but it has also given rise to a bistable systems with an enhanced energetic separation between states and an acceleration of the reorganization processes. Thus far, rotaxane 2[PF6] presents the fastest switching cycle reported to date in copper-interlocked dynamic systems.
- Coronado, Eugenio,Gavina, Pablo,Ponce, Julia,Tatay, Sergio
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p. 6939 - 6950
(2014/06/09)
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- Effect of metal complexation on the conductance of single-molecular wires measured at room temperature
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The present work aims to give insight into the effect that metal coordination has on the room-temperature conductance of molecular wires. For that purpose, we have designed a family of rigid, highly conductive ligands functionalized with different termina
- Ponce, Julia,Arroyo, Carlos R.,Tatay, Sergio,Frisenda, Riccardo,Gavi?a, Pablo,Aravena, Daniel,Ruiz, Eliseo,Van Der Zant, Herre S. J.,Coronado, Eugenio
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supporting information
p. 8314 - 8322
(2014/06/24)
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- NEW (TRIORGANOSILYL)ALKYNES AND THEIR DERIVATIVES AND A NEW CATALYTIC METHOD FOR OBTAINING NEW AND CONVENTIONAL SUBSTITUTED (TRIORGANOSILYL)ALKYNES AND THEIR DERIVATIVES
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The present invention relates to new (triorganosilyl)alkynes and their derivatives having general formula 1 R1—C≡C—Z (I) In its second aspect, this invention relates to a new selective method for the preparation of new and conventional (triorga
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Paragraph 0161; 0169-0175
(2014/02/15)
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- Palladium Catalyzed Reactions Executed on Solid-Phase Peptide Synthesis Supports for the Production of Self-Assembling Peptides Embedded with Complex Organic Electronic Subunits
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Methods to synthesize self-assembling peptides embedded with complex organic electronic subunits are provided.
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(2014/05/07)
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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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supporting information
p. 7862 - 7872
(2013/08/23)
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- Encapsulation-induced remarkable stability of a hydrogen-bonded heterocapsule
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Remarkably enhanced stability of the self-assembled hydrogen-bonded heterocapsule 1×2 by the encapsulation of 1,4-bis(1-propynyl)benzene 3 a was found with Ka=1.14×109 M-1 in CDCl3 and Ka2=1.59×108 M-2 in CD3OD/CDCl3 (10 % v/v) at 298 K. The formation of 3 a(1×2) was enthalpically driven (ΔH°0 and ΔS°0) and there was a unique inflection point in the correlation between ΔH° versus ΔS° as a function of polar solvent content. The ab initio calculations revealed that favorable guest-capsule dispersion and electrostatic interactions between the acetylenic parts (triple bonds) of 3 a and the aromatic inner space of 1×2, as well as less structural deformation of 1×2 upon encapsulation of 3 a, play important roles in the remarkable stability of 3 a(1×2). Copyright
- Ichihara, Keisuke,Kawai, Hidetoshi,Togari, Yuka,Kikuta, Emi,Kitagawa, Hitomi,Tsuzuki, Seiji,Yoza, Kenji,Yamanaka, Masamichi,Kobayashi, Kenji
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supporting information
p. 3685 - 3692
(2013/04/10)
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- Synthesis and biological evaluation of new bis-indolone-N-oxides
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A series of bis-indolone-N-oxides, 1a-f, was prepared from bis(ethynyl)benzenes and o-halonitroaryls and studied for their in vitro antiplasmodial activities against Plasmodium falciparum and representative strains of bacteria and candida as well as for their cytotoxicity against a human tumor cell line (MCF7). They did not cause any haemolysis (300 μg mL-1). Of the synthesized bis-indolones, compound 1a had the most potent antiplasmodial activity (IC50 = 0.763 μmol L-1 on the FcB1 strain) with a selectivity index (CC50 MCF7/IC 50 FcB1) of 35.6. No potency against the tested microbial strains was observed.
- Najahi, Ennaji,Valentin, Alexis,Tene, Nathan,Treilhou, Michel,Nepveu, Francoise
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- NEW (TRIORGANOSILYL)ALKYNES AND THEIR DERIVATIVES AND A NEW CATALYTIC METHOD FOR OBTAINING NEW AND CONVENTIONAL SUBSTITUTED (TRIORGANOSILYL)ALKYNES AND THEIR DERIVATIVES
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The present invention relates to new (triorganosilyl)alkynes and their derivatives having general formula 1 R1-C≡C-Z (I) In its second aspect, this invention relates to a new selective method for the preparation of new and conventional (triorga
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Page/Page column 14
(2012/07/14)
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- Calix[4]bis(spirodienone) as a versatile synthon for upper rim alkoxylation of calixarenes and synthesis of novel triazole-based biscalixarene by 'CuAAC' chemistry
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The spiro rings of calix[4]bis(spirodienone) have been opened up using various bromofunctionalised alcohols employing a novel ipso nucleophilic substitution of tert-butyl groups by alkoxy groups. Additionally, a route has been paved towards the preparation of triazole-linked biscalixarene via the copper(I)-catalysed modern version of classical Huisgen 1,3-dipolar cycloaddition of alkynyl calixarene and azidocalixarene, derived from the above-mentioned bromo-substituted calixarene.
- Thulasi, Sreeja,Savithri, Anupriya,Varma, Ramavarma Luxmi
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experimental part
p. 501 - 508
(2012/06/18)
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- Synthesis of substituted linear Ter- and quaterphenyls via dewar benzenes
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Tetramethylcyclobutadiene-AlClcomplex reacted with bisalkynes possessing phenylene and biphenylene spacer giving rise to mono- and bis-Dewar benzenes. The rearrangement of the bis-Dewar benzene derivatives under thermal conditions (150 C) yielded the corr
- Janková, ?těpánka,Hybelbauerová, Simona,Kotora, Martin
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scheme or table
p. 396 - 398
(2011/04/22)
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- From molecular to macroscopic engineering: Shaping hydrogen-bonded organic nanomaterials
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The self-assembly and self-organization behavior of chromophoric acetylenic scaffolds bearing 2,6-bis(acetylamino)pyridine (1, 2) or uracyl-type (3-9) terminal groups has been investigated by photophysical and microscopic methods. Systematic absorption and luminescence studies show that 1 and 2, thanks to a combination of solvophilic/solvophobic forces and π-π stacking interactions, undergo self-organization in apolar solvents (i.e., cyclohexane) and form spherical nanoparticles, as evidenced by wide-field optical microscopy, TEM, and AFM analysis. For the longer molecular module, 2, a more uniform size distribution is found (80-200nm) compared to 1 (20-1000nm). Temperature scans in the range 283-353K show that the self-organized nanoparticles are reversibly formed and destroyed, being stable at lower temperatures. Molecular modules 1 and 2 were then thoroughly mixed with the complementary triply hydrogen-bonding units 3-9. Depending on the specific geometrical structure of 3-9, different nanostructures are evidenced by microscopic investigations. Combination of modules 1 or 2 with 3, which bears only one terminal uracyl unit, leads to the formation of vesicular structures; instead, when 1 is combined with bis-uracyl derivative 4 or 5, a structural evolution from nanoparticles to nanowires is observed. The length of the wires obtained by mixing 1 and 4 or 1 and 5 can be controlled by addition of 3, which prompts transformation of the wires into shorter rods. The replacement of linear system 5 with the related angular modules 6 and 7 enables formation of helical nanostructures, unambiguously evidenced by AFM. Finally, thermally induced self-assembly was studied in parallel with modules 8 and 9, in which the uracyl recognition sites are protected with tert-butyloxycarbonyl (BOC) groups. This strategy allows further control of the self-assembly/self-organization process by temperature, since the BOC group is completely removed on heating. Microscopy studies show that the BOC-protected ditopic modules 8 self-assemble and self-organize with 1 into ordered linear nanostructures, whereas BOC-protected tritopic system 9 gives rise to extended domains of circular nano-objects in combination with 1.
- Yoosaf,Llanes-Pallas, Anna,Marangoni, Tomas,Belbakra, Abdelhalim,Marega, Riccardo,Botek, Edith,Champagne, Beno?t,Bonifazi, Davide,Armaroli, Nicola
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supporting information; scheme or table
p. 3262 - 3273
(2011/04/24)
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- Silylative coupling of terminal alkynes with iodosilanes: New catalytic activation of sp-hybridized carbon-hydrogen bonds
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The [{Ir(μ-Cl)(CO)2}2] (I)-catalyzed reaction of terminal alkynes and diynes with Me3SiI with the aid of NEt(i-Pr)2 occurs smoothly, leading to the formation of mono- and bis-silyl-functionalized alkynyl derivat
- Kownacki, Ireneusz,Marciniec, Bogdan,Dudziec, Beata,Kubicki, MacIej
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experimental part
p. 2539 - 2545
(2011/06/27)
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- New soluble rigid rod copolymers comprising alternating 2-amino-pyrimidine and phenylene repeat units: Syntheses, characterization, optical and electrochemical properties
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A new type - π-conjugated copolymers of 2-amino-pyrimidine was prepared between 2-amino-4,6-diiodidepyrimidine and 1,4-dibromo-2,5-dialkoxybenzene by Sonogashira polycondensation. The structures of the copolymers were elucidated by FT-IR, 1H NMR and 13C NMR, fluorescence spectroscopy, gel permeation chromatography, thermal analysis and element analysis. The derived polymers were soluble in common organic solvents and trifloroacetic acid and exhibited good thermal stability. They emitted green light under UV irradiation in solid state and blue or green light in solution phase, respectively. Electrochemical behavior of these new polymers depicted facile p-doping and good electron-transporting properties. These polymers displayed bathochromic shift when protonated with CH3SO3H acid in chloroform solutions or m-cresol solutions and the red-shifted peaks were observed from 490 nm to 652 nm. XRD patterns of copolymers showed that the intensity of peaks was enhanced with increasing alkyloxy chain length.
- Mamtimin, Xirali,Matsidik, Rukiya,Nurulla, Ismayil
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scheme or table
p. 437 - 446
(2011/02/24)
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- Mixed [2.2]cyclophanes of pyrene and benzene
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An examination of the literature on [2.2]cyclophanes reveals a loose relationship between the relative sizes of the two 'half-cyclophanes' (as measured by the parameter Δd) and the limitations of the dominant general synthetic approaches. Direct coupling methods tend to be successful only for systems with Δd values below 1.0 A, whereas ring-contraction-based approaches are usually viable for systems with Δd values up to 2.0.A For the very few known systems with Δd values greater than 2.0A, aromatization-based approaches are the only ones that have been successful. The syntheses of two [2.2]cyclophanes with very large Δd values, [2]paracyclo[2](2,7)pyrenophane (17) (Δd = 4.25A) and [2]metacyclo[2](2,7)pyrenophane (18) (d≤5.04A) are presented here. The syntheses hinge on a valence isomerization/dehydrogenation reaction. The crystallographically determined bend angle, θ, for 18 is 96.1°. Cyclophane 18 undergoes a degenerate conformational flip, the energy barrier for which was determined to be 18.9 kcal mol-1 by DNMR. CSIRO 2010.
- Vermeij, Rudolf J.,Miller, David O.,Dawe, Louise N.,Aprahamian, Ivan,Sheradsky, Tuvia,Rabinovitz, Mordecai,Bodwell, Graham J.
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experimental part
p. 1703 - 1716
(2011/09/16)
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- Selective gas adsorption in the flexible metal-organic frameworks Cu(BDTri)L (L = DMF, DEF)
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Use of the ditopic ligand 1,4benzenedi(1H-1,2,3-triazole) (H 2BDTri) enabled isolation of two new three-dimensional metal-organic frameworks of formulae Cu(BDTri)L in which L = DMF (1) and diethylformamide (DEF; 2). These compounds have the same primary structure, featuring one-dimensional channels with the bridging DMF or DEF molecules pointing into the cavity. Upon exposure to solvent vapors, both display a reversible flexibility, as characterized by single-crystal to single-crystal phase transitions in 1. The O2 adsorption isotherms for the compounds show a twostep adsorption behavior associated with a permanent microporosity and a pore-opening process. In the case of N2 adsorption, only 1 exhibits a two-step adsorption isotherm, whereas 2 does not present any pore opening, demonstrating that design of a flexible framework cavity can control the pore opening and thereby possibly enhance O2/ N2 separation.
- Demessence, Aude,Long, Jeffrey R.
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supporting information; experimental part
p. 5902 - 5908
(2010/09/09)
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- Solvent-free Sonogashira coupling reaction via high speed ball milling
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Herein, we report on the solvent-free Sonogashira reaction utilizing high speed ball milling. Sonogashira coupling of a variety of para substituted aryl halides were performed with trimethylsilylacetylene or phenylacetylene. We observed that iodo and bromo substituted aromatics successfully undergo Sonogashira coupling. However, chloro and fluoro substituted aryl compounds were unreactive. Conducting the coupling reaction in the absence of copper iodide led to low yields. Alternately, if the reaction is conducted with a copper ball in a copper vial in lieu of copper iodide, the coupling product is observed in high yields. This demonstrates the first report on the use of the vial and ball material as a catalyst in a ball milled chemical reaction. The Royal Society of Chemistry 2009.
- Fulmer, Dennis A.,Shearouse, William C.,Medonza, Shareika T.,MacK, James
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experimental part
p. 1821 - 1825
(2011/02/24)
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- Synthesis and quantum chemical study of PDI derivatives with phenylalkynyl groups at the bay position
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Six new perylenetetracarboxylic diimide (PDI) compounds were prepared by introducing alkynyl or alkynylphenyl groups with different length to the bay position of PDI ring. The UV-vis absorption and emission spectra of these new compounds were recorded. Th
- Wang, Delou,shi, Yan,Zhao, Chuntao,Liang, Baolong,Li, Xiyou
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experimental part
p. 245 - 253
(2010/04/01)
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- STRUCTURE, SYNTHESIS, AND APPLICATIONS FOR OLIGO PHENYLENE ETHYNYLENES
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Novel compounds generally referred to herein as cationic oligomeric phenylene ethynylenes (OPEs), methods of synthesizing OPEs and various uses for the OPEs are described. The compounds can be synthesized in both symmetrical (S-OPE) and non- symmetrical (N-OPE) forms. Suitable uses include sensor and biocidal applications. Reusable structures incorporating the OPEs that are able to capture and release biological species of interest are also described.
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Page/Page column 10
(2010/01/30)
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- Unique twisted ribbons generated by self-assembly of oligo(p-phenylene ethylene) bearing dimeric bile acid pendant groups
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A series of novel oligo(pphenylene ethynylene) (OPE) derivatives bearing dimeric cholic acid (OPE1), deoxycholic acid (OPE2) and lithocholic acid (OPE3) was synthesized. The self-assembly behavior of these derivatives were systematically studied and compared in a THF/water solvent mixture. The addition of water to THF can induce the helical stacking of oligo(p-phenylene ethylene) bearing dimeric deoxycholic acid end groups, which leads to highly interesting twisted assemblies. Variation of the bile acid group led to nanostructures with drastically different morphologies. The application of spectroscopy in combination with X-ray diffraction techniques provided a reasonable view of the final self-assembled structures. The observed distinctive aggregate shapes and the preference in the type of molecular packing of these steroid-OPE conjugates are attributed to the subtle differences in their molecular features.
- Li, Yan,Li, Guangtao,Wang, Xinyan,Li, Weina,Su, Zhixiang,Zhang, Yihe,Ju, Yong
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scheme or table
p. 6399 - 6407
(2010/02/28)
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- Organosilane compound and organosilica obtained therefrom
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Provided is an organosilane compound expressed by any one of the following general formulae (1) to (7): (wherein: Ar represents a phenylene group or the like; R1 represents a hydrogen atom or the like; R2 to R8 each represent a methyl group or the like; n represents an integer in a range from 0 to 2; m represents an integer of 1 or 2; L represents a single bond or the like; X represents a hydrogen atom or the like; and Y represents a hydrogen atom or the like).
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Page/Page column 25
(2008/12/07)
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- Poly(p-phenylene ethynylene)s with facially amphiphilic pendant groups: Solvatochromism and supramolecular assemblies
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Novel functionalized poly(p-phenylene ethynylene)s (PPEs) bearing facially amphiphilic cholic and deoxycholic acid units are synthesized by a Pd-catalyzed Sonogashira cross-coupling reaction. Some interesting properties, particularly their optical and self-assembly characteristics, are unraveled. The PPEs that carry bile acid substituents exhibit remarkable solvatochromism in a wide range of solvent systems, and judicious choice of the solvents can adjust the size and morphology of the formed nanoscale supramolecular aggregates. The incorporation of these naturally occurring building blocks can also impart bio-compatibility to the conjugated system and stimulate the growth of living cells.
- Li, Yan,Li, Guangtao,Wang, Xinyan,Lin, Changxu,Zhang, Yihe,Ju, Yong
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scheme or table
p. 10331 - 10339
(2009/10/23)
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- Electrical properties of 1,4-bis(4-(phenylethynyl)phenylethynyl)benzene and its application for organic light emitting diodes
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We found that a phenylene ethynylene derivative, 1,4-bis(4-(phenylethynyl) phenylethynyl)benzene (BPPB), provides very high photoluminescence efficiency both in solution (ΦPL = 95 ± 3%) and thin films (ΦPL = 71 ± 3%); further, we observed blue electroluminescence (EL) of λEL (max) ～470 and 510 nm with an external EL efficiency of ηEL ～0.53% and maximum luminance of ～70000 cd m-2 at current density of ～2 A cm -2 with BPPB as an emitter; also we identified that BPPB functions as a hole transport layer in organic light emitting diodes. The Royal Society of Chemistry.
- Fenenko, Larysa,Shao, Guang,Orita, Akihiro,Yahiro, Masayuki,Otera, Junzo,Svechnikov, Sergei,Adachi, Chihaya
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p. 2278 - 2280
(2007/12/27)
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- Design principles to tune the optical properties of 1,3,4-oxadiazole- containing molecules
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We have synthesized a series of oxadiazole compounds and ethynylene analogs. Our data reveal that the ring is both optically transparent in the visible range and fully conjugating while we have also discovered the presence of a non-radiative mechanism active in molecules containing common para-dialkoxy substituents adjacent to the oxadiazole ring(s). This structure leads to a greatly reduced quantum yield, in our example dropping from 95.0% to 48.0%. Through our thorough study we have revealed evidence that this is the result of a repulsive interaction between the oxadiazole and the adjacent alkoxy oxygen atom, which we believe prevents excited-state planarity. This quantum yield reduction is preventable through the design principles presented here. The Royal Society of Chemistry 2007.
- Bolton, Onas,Kim, Jinsang
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p. 1981 - 1988
(2008/02/08)
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- Evidence for the assembly of carboxyphenylethynyl zinc porphyrins on nanocrystalline TiO2 surfaces
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UV-visible absorption and AFM studies suggest that carboxyphenylethynyl zinc porphyrins aggregate on nanocrystalline TiO2 surfaces in an H-type fashion. The Royal Society of Chemistry 2006.
- Lo, Chen-Fu,Luo, Liyang,Diau, Eric Wei-Guang,Chang, I.-Jy,Lin, Ching-Yao
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p. 1430 - 1432
(2008/02/03)
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- Investigation of two-photon absorption behavior in symmetrical acceptor-π-acceptor derivatives with dimesitylboryl end-groups. Evidence of new engineering routes for TPA/transparency trade-off optimization
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Investigations of the non-linear optical properties of a novel series of A-π-A quadrupoles, based on dimesitylboron end-groups, reveal the promising potential of elongated vinylboranes derivatives for combined enhanced two-photon absorption cross-section and improved transparency in the visible region. In addition, the excited state lifetime can be significantly enhanced in A-π-A′-π-A derivatives. This opens a new route towards optimized molecules for optical power limiting. The Owner Societies 2005.
- Chariot, Marina,Porres, Laurent,Entwistle, Christopher D.,Beeby, Andrew,Marder, Todd B.,Blanchard-Desce, Mireille
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p. 600 - 606
(2007/10/03)
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- A simple "palladium-free" synthesis of phenyleneethynylene-based molecular materials revisited
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Nucleophilic attack of acetylide anions at the two carbonyl moieties of para-quinones readily affords the corresponding diols. Subsequent reduction with stannous chloride affords a number of useful compounds, including 1,4-bis[(trimethylsilyl)ethynyl]benzene, 1,4-bis[(trimethylsilyl)ethynyl] naphthalene and 9,10-bis[(trimethylsilyl)ethynyl]anthracene. Sequential attack by different acetylide anions followed by reduction provides a useful route to differentially substituted compounds including 1-[(4-nonyloxyphenyl)ethynyl]-4- (phenylethynyl)benzene, a new luminescent liquid-crystalline material. The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2005.
- Lydon, Donocadh P.,Porres, Laurent,Beeby, Andrew,Marder, Todd B.,Low, Paul J.
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p. 972 - 976
(2007/10/03)
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- New synthetic applications of indium organometallics in cross-coupling reactions
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The use of indium organometallics in multifold and sequential cross-coupling reactions is reported. Triorganoindium reagents (R3In) react, under palladium catalysis, with oligohaloarenes affording the multiple cross-coupling products in a single operation. In the reaction, the three organic groups (alkyl, aryl, alkenyl or alkynyl) attached to indium are efficiently transferred to the electrophile, with only a slight excess of organometallic reagent. We demonstrate that indium organometallics are useful reagents for sequential cross-coupling reactions. This reaction illustrates the high chemoselectivity of R3In. Georg Thieme Verlag Stuttgart.
- Pena, Miguel A.,Perez Sestelo, Jose,Sarandeses, Luis A.
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p. 485 - 492
(2007/10/03)
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- The CA.M lattice revisited. Gel formation from a linear bis-isocyanuric acid and 2-amino-4,6-bis-(4-tert-butylphenylamino)-1,3,5-triazine
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Five bis(isocyanuric) acid dimers have been prepared and characterised. The introduction of flexible alkyl chains was necessary to aid solubility. On mixing with N,N-bis(4-tert-butyphenyl)melamine in THF followed by slow evaporation, a viscous gel can form which is interpreted as evidence for the assembly of an infinite 2-D hydrogen bonded network.
- Plater, M. John,Sinclair, James P.,Aiken, Stuart,Gelbrich, Thomas,Hursthouse, Michael B.
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p. 6385 - 6394
(2007/10/03)
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- Synthesis of buta-1,3-diyne-bridged macrocycles with (Z)-1,4-diethynyl-1,4-dimethoxycyclohexa-2,5-diene as the building block
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(Z)-1,4-Diethynyl-1,4-dimethoxycyclohexa-2,5-diene has been used as a building block for the synthesis of two novel macrocycles containing buta-1,3-diyne units as bridges. The tetrayne derivative 5c has been structurally characterized by single crystal X-ray crystallographic data. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.
- Srinivasan, Manivannan,Sankararaman, Sethuraman,Hopf, Henning,Varghese, Babu
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p. 660 - 665
(2007/10/03)
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- Improved and new syntheses of potential molecular electronics devices
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New syntheses of ethyl and nitro substituted oligo(phenylene ethynylene)s (OPEs) have been developed. To further explore whether the presence of nitro functionality in OPEs leads to switching and memory capabilities, new nitro substituted OPEs have been designed and synthesized. An isatogen-based system, a structure that is isomeric to the nitro OPE, has been synthesized. Additionally, pyridine-based and chromium-based compounds have been synthesized. We surmise that redox reactions of these candidates may impart switching capabilities and electrochemical studies are shown. U-shaped OPEs were synthesized to inhibit leakage of metals deposited during formation of top contacts on self-assembled monolayers (SAMs). The OPEs contain either thiol-based moieties or isonitrile groups to enable formation of SAMs on metal substrates.
- Price Jr., David W.,Dirk, Shawn M.,Maya, Francisco,Tour, James M.
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p. 2497 - 2518
(2007/10/03)
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- Synthesis, electronic structure, and electron transfer dynamics of (aryl)ethynyl-bridged donor-acceptor systems
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The ET dynamics of a series of donor-spacer-acceptor (D-Sp-A) systems featuring (porphinato)zinc(II), (aryl)ethynyl bridge, and arene diimide units were investigated by pump-probe transient absorption spectroscopy. Analysis of these data within the context of the Marcus-Levich-Jortner equation suggests that the π-conjugated (aryl)ethynyl bridge plays an active role in the charge recombination (CR) reactions of these species by augmenting the extent of (porphinato)zinc(II) cation radical electronic delocalization; this increase in cation radical size decreases the reorganization energy associated with the CR reaction and thereby attenuates the extent to which the magnitudes of the CR rate constants are solvent dependent. The symmetries of porphyrin-localized HOMO and HOMO-1, the energy gap between these two orbitals, and D-A distance appear to play key roles in determining whether the (aryl)ethynyl bridge simply mediates electronic superexchange or functions as an integral component of the D and A units.
- Redmore, Naomi P.,Rubtsov, Igor V.,Therien, Michael J.
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p. 8769 - 8778
(2007/10/03)
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- Polyfluorenes with polyphenylene dendron side chains: Toward non-aggregating, light-emitting polymers
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A polyfluorene 12 has been prepared in which bulky polyphenylene dendrimer substituents suppress formation of long wavelength emitting aggregates, thus giving a polymer with pure blue emission. Absorption-and emission spectra and molecular modeling confirm that the bulky dendrimer side chains do not cause extra torsion between the fluorene units. New polyfluorenes with 9,9-diaryl substituents have been prepared to determine the minimum size of substituent necessary for aggregation suppression. An LED using 12 has been demonstrated to produce blue emission with onset voltages below 4 V.
- Setayesh,Grimsdale,Weil,Enkelmann,Muellen,Meghdadi,List,Leising
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p. 946 - 953
(2007/10/03)
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- Synthesis and preliminary testing of molecular wires and devices
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Presented here are several convergent synthetic routes to conjugated oligo(phenylene ethynylene)s. Some of these oligomers are free of functional groups, while others possess donor groups, acceptor groups, porphyrin interiors, and other heterocyclic interiors for various potential transmission and digital device applications. The syntheses of oligo(phenylene ethynylene)s with a variety of end groups for attachment to numerous metal probes and surfaces are presented. Some of the functionalized molecular systems showed linear, wire-like, current versus voltage (I(V)) responses, while others exhibited nonlinear I(V) curves for negative differential resistance (NDR) and molecular random access memory effects. Finally, the syntheses of functionalized oligomers are described that can form self-assembled monolayers on metallic electrodes that reduce the Schottky barriers. Information from the Schottky barrier studies can provide useful insight into molecular alligator clip optimizations for molecuar electronics.
- Tour, James M.,Rawlett, Adam M.,Kozaki, Masatoshi,Yao, Yuxing,Jagessar, Raymond C.,Dirk, Shawn M.,Price, David W.,Reed, Mark A.,Zhou, Chong-Wu,Chen, Jia,Wang, Wenyong,Campbell, Ian
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p. 5118 - 5134
(2007/10/03)
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- Nonplanar Aromatic Compounds. 6. [2]Paracyclo[2](2,7)pyrenophane. A Novel Strained Cyclophane and a First Step on the Road to a "Voegtle" Belt
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(formula presented) A benzene ring nestled into the concave face of a bent pyrene characterizes the title compound in the crystal. The synthesis of this compound was accomplished using the valence isomerization-dehydrogenation (VID) method and marks the official launch of our journey en route to aromatic belts first proposed by Prof. Voegtle.
- Bodwell, Graham J.,Miller, David O.,Vermeij, Rudolf J.
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p. 2093 - 2096
(2007/10/03)
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