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François Mathey - One of the best experts on this subject based on the ideXlab platform.
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The Original Reactivity of a Phosphole-Substituted Fischer Carbene Complex
2016Co-Authors: Rakesh Ganguly, François MatheyAbstract:In an unprecedented transformation, a Phosphole-substituted Fischer carbene complex reacts with styrene to give an annelated Phosphole derivative
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Reaction of Phospholes with Aldimines: A One‐Step Synthesis of Chelating, Alpha‐C2‐Bridged BiPhospholes.
ChemInform, 2015Co-Authors: Kang Zhao, Rongqiang Tian, Zheng Duan, François MatheyAbstract:Phospholes react with aldimines at 170 °C in the presence of mild Lewis acids to give C2-bridged biPhospholes in good yields. The mechanism includes a series of [1,5] shifts of the P-substituents around the Phosphole ring, a P–H + aldimine condensation, and the formation of a transient three-membered ring that dimerizes.
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Reaction of Phospholes with Aldimines: A One-Step Synthesis of Chelating, Alpha-C2-Bridged BiPhospholes.
Organic letters, 2015Co-Authors: Kang Zhao, Rongqiang Tian, Zheng Duan, François MatheyAbstract:Phospholes react with aldimines at 170 °C in the presence of mild Lewis acids to give C2-bridged biPhospholes in good yields. The mechanism includes a series of [1,5] shifts of the P-substituents around the Phosphole ring, a P–H + aldimine condensation, and the formation of a transient three-membered ring that dimerizes.
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The Original Reactivity of a Phosphole-Substituted Fischer Carbene Complex
Organometallics, 2013Co-Authors: Rakesh Ganguly, François MatheyAbstract:In an unprecedented transformation, a Phosphole-substituted Fischer carbene complex reacts with styrene to give an annelated Phosphole derivative.
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Electrochemical Decomplexation of Phosphine-Pentacarbonyltungsten Complexes: The Phosphole Case
Organometallics, 2004Co-Authors: Dmitry G. Yakhvarov, Yulia H. Budnikova, Ngoc Hoa Tran Huy, Louis Ricard, François MatheyAbstract:Electrochemical reduction of Phosphole P-W(CO)5 complexes affords the free Phospholes in good yields. This technique allows the decomplexation of a 2-ethoxy-4-keto-4,5-dihydroPhosphole, which has been characterized by X-ray crystal structure analysis of its P-sulfide.
Hiroshi Imahori - One of the best experts on this subject based on the ideXlab platform.
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Phosphole-Thiophene Hybrid: A Dual Role of Dithieno[3,4- b:3',4'- d]Phosphole as Electron Acceptor and Electron Donor.
The Journal of organic chemistry, 2018Co-Authors: Tomohiro Higashino, Yoshihiro Matano, Keiichi Ishida, Takaharu Satoh, Hiroshi ImahoriAbstract:We have synthesized dithieno[3,4-b:3′,4′-d]Phosphole derivatives as a new type of thiophene-fused Phospholes. These dithienoPhospholes were found to show intramolecular charge transfer interactions by introducing electron-donating or -withdrawing groups on the peripheral aryl groups. Namely, they exhibit the unique hybrid character of electron-withdrawing Phosphole and electron-donating thiophene.
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Phosphole–Thiophene Hybrid: A Dual Role of Dithieno[3,4‑b:3′,4′‑d]Phosphole as Electron Acceptor and Electron Donor
2018Co-Authors: Tomohiro Higashino, Yoshihiro Matano, Keiichi Ishida, Takaharu Satoh, Hiroshi ImahoriAbstract:We have synthesized dithieno[3,4-b:3′,4′-d]Phosphole derivatives as a new type of thiophene-fused Phospholes. These dithienoPhospholes were found to show intramolecular charge transfer interactions by introducing electron-donating or -withdrawing groups on the peripheral aryl groups. Namely, they exhibit the unique hybrid character of electron-withdrawing Phosphole and electron-donating thiophene
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synthesis and structure property relationships of 2 2 bis benzo b Phosphole and 2 2 benzo b Phosphole benzo b heterole hybrid π systems
Chemistry: A European Journal, 2012Co-Authors: Yukiko Hayashi, Yoshihiro Matano, Yoshifumi Kimura, Kayo Suda, Yoshihide Nakao, Hiroshi ImahoriAbstract:The first comprehensive study of the synthesis and structure-property relationships of 2,2'-bis(benzo[b]Phosphole)s and 2,2'-benzo[b]Phosphole-benzo[b]heterole hybrid π systems is reported. 2-Bromobenzo[b]Phosphole P-oxide underwent copper-assisted homocoupling (Ullmann coupling) and palladium-catalyzed cross-coupling (Stille coupling) to give new classes of benzo[b]Phosphole derivatives. The benzo[b]Phosphole-benzo[b]thiophene and -indole derivatives were further converted to P,X-bridged terphenylenes (X = S, N) by a palladium-catalyzed oxidative cycloaddition reaction with 4-octyne through the C(β)-H activation. X-ray analyses of three compounds showed that the benzo[b]Phosphole-benzo[b]heterole derivatives have coplanar π planes as a result of the effective conjugation through inter-ring C-C bonds. The π-π* transition energies and redox potentials of the cis and trans isomers of bis(benzo[b]Phosphole) P-oxide are very close to each other, suggesting that their optical and electrochemical properties are little affected by the relative stereochemistry at the two phosphorus atoms. The optical properties of the benzo[b]Phosphole-benzo[b]heterole hybrids are highly dependent on the benzo[b]heterole subunits. Steady-state UV/Vis absorption/fluorescence spectroscopy, fluorescence lifetime measurements, and theoretical calculations of the non-fused and acetylene-fused benzo[b]Phosphole-benzo[b]heterole π systems revealed that their emissive excited states consist of two different conformers in rapid equilibrium.
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Synthesis and Structure–Property Relationships of 2,2′‐Bis(benzo[b]Phosphole) and 2,2′‐Benzo[b]Phosphole–Benzo[b]heterole Hybrid π Systems
Chemistry (Weinheim an der Bergstrasse Germany), 2012Co-Authors: Yukiko Hayashi, Yoshihiro Matano, Yoshifumi Kimura, Kayo Suda, Yoshihide Nakao, Hiroshi ImahoriAbstract:The first comprehensive study of the synthesis and structure-property relationships of 2,2'-bis(benzo[b]Phosphole)s and 2,2'-benzo[b]Phosphole-benzo[b]heterole hybrid π systems is reported. 2-Bromobenzo[b]Phosphole P-oxide underwent copper-assisted homocoupling (Ullmann coupling) and palladium-catalyzed cross-coupling (Stille coupling) to give new classes of benzo[b]Phosphole derivatives. The benzo[b]Phosphole-benzo[b]thiophene and -indole derivatives were further converted to P,X-bridged terphenylenes (X = S, N) by a palladium-catalyzed oxidative cycloaddition reaction with 4-octyne through the C(β)-H activation. X-ray analyses of three compounds showed that the benzo[b]Phosphole-benzo[b]heterole derivatives have coplanar π planes as a result of the effective conjugation through inter-ring C-C bonds. The π-π* transition energies and redox potentials of the cis and trans isomers of bis(benzo[b]Phosphole) P-oxide are very close to each other, suggesting that their optical and electrochemical properties are little affected by the relative stereochemistry at the two phosphorus atoms. The optical properties of the benzo[b]Phosphole-benzo[b]heterole hybrids are highly dependent on the benzo[b]heterole subunits. Steady-state UV/Vis absorption/fluorescence spectroscopy, fluorescence lifetime measurements, and theoretical calculations of the non-fused and acetylene-fused benzo[b]Phosphole-benzo[b]heterole π systems revealed that their emissive excited states consist of two different conformers in rapid equilibrium.
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α α diarylacenaphtho 1 2 c Phosphole p oxides divergent synthesis and application to cathode buffer layers in organic photovoltaics
Chemistry-an Asian Journal, 2012Co-Authors: Yoshihiro Matano, Tooru Miyajima, Arihiro Saito, Yuto Suzuki, Seiji Akiyama, Saika Otsubo, Emi Nakamoto, Shinji Aramaki, Hiroshi ImahoriAbstract:A divergent method for the synthesis of α,α'-diarylacenaphtho[1,2-c]Phosphole P-oxides has been established; α,α'-dibromoacenaphtho[c]Phosphole P-oxide, which was prepared through a Ti(II)-mediated cyclization of 1,8-bis(trimethylsilylethynyl)naphthalene, underwent a Stille coupling with three different kinds of aryltributylstannanes to afford the α,α'-diarylacenaphtho[c]Phosphole P-oxides in moderate to good yields. X-ray crystallographic analyses and UV/Vis absorption/fluorescence measurements have revealed that the degree of π-conjugation, the packing motif, the electron-accepting ability, and the thermal stability of the acenaphtho[c]Phosphole π-systems are finely tunable with the α-aryl substituents. All the P=O and P=S derivatives exhibited high stability in their electrochemically reduced state. To use this class of arene-fused Phosphole π-systems as n-type semiconducting materials, we evaluated device performances of the bulk heterojunction organic photovoltaics (OPV) that consist of poly(3-hexylthiophene), an indene-C(70) bisadduct, and a cathode buffer layer. The insertion of the diarylacenaphtho[c]Phosphole P-oxides as the buffer layer was found to improve the power conversion efficiency of the polymer-based OPV devices.
Thomas Baumgartner - One of the best experts on this subject based on the ideXlab platform.
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Structure–Property Studies Toward the Stimuli-Responsive Behavior of Benzyl–Phospholium Acenes
2016Co-Authors: Yi Ren, Thomas BaumgartnerAbstract:A series of new phospholium acenes, quaternized with benzyl groups, was synthesized. Both different π-conjugated backbones and electron-donating/-withdrawing benzyl groups were systematically studied to reveal details on the nature of their structural dynamics. Extensive NMR studies (including variable concentration/temperature and 2D) suggested that the systems undergo intramolecular conformation changes in solution that are strongly affected by the electronic nature of the benzyl group, and thereby significantly affecting the Phosphole-typical σ*−π* interaction. This class of “smart” Phosphole system exhibits enhanced emission in the solid state and at low temperature in solution, due to aggregation-induced enhanced emission (AIEE). The dynamic features of these smart Phospholes also endow the systems with external-stimuli (thermal and mechanical force) responsive photophysical properties. Crystallographic studies and theoretical calculations confirmed that the thermal response of the phospholium system is mainly due to the conformation changes in solution, while the mechanical response of the system can be attributed to both the intramolecular conformation and the intermolecular organization changes in the solid state
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Synthesis and Properties of Cholesteric Click-Phospholes
Organic letters, 2014Co-Authors: Jian-bin Lin, Wang Hay Kan, Simon Trudel, Thomas BaumgartnerAbstract:Inspired by naturally occurring helical supramolecular architectures, a series of chiral conjugated Phospholes with a cholesteryl pendant have been synthesized and characterized. The photophysically and electrochemically active conjugated Phosphole species can act as dopants for the formation of chiral liquid crystals. The supramolecular structures were found to be tunable by careful choice of the conjugated headgroup as well as the rigidity of the linker of the new cholesteric Phospholes.
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dithiazolo 5 4 b 4 5 d Phosphole a highly luminescent electron accepting building block
Chemistry: A European Journal, 2013Co-Authors: Alva Y Y Woo, Javier Boraugarcia, Thomas BaumgartnerAbstract:A family of highly emissive dithiazolo[5,4-b:4',5'-d]Phospholes has been designed and synthesized. The structures of two trivalent P species, as well as their corresponding P oxides, have been confirmed by X-ray crystallography. The parent dithiazolo[5,4-b:4',5'-d]Phosphole oxide exhibits strong blue photoluminescence at λem = 442 nm, with an excellent quantum yield efficiency of ϕPL = 0.81. The photophysical properties of these compounds can be easily tuned by extension of the conjugation and modification of the phosphorus center. Compared with the established dithieno[3,2-b:2',3'-d]Phosphole system, the incorporation of electronegative nitrogen atoms leads to significantly lowered frontier orbital energy levels, as validated by both electrochemistry and theoretical calculations, thus suggesting that the dithiazolo[5,4-b:4',5'-d]Phospholes are valuable, air-stable, n-type conjugated materials. These new building blocks have been further applied to the construction of an extended oligomer with fluorene. Extension of the dithiazoloPhosphole core with triazole units through click reactions also provides a suitable N,N-chelating moiety for metal binding and a representative molecular species was successfully used as a selective colorimetric and fluorescent sensor for Cu(II) ions.
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Structure-property studies toward the stimuli-responsive behavior of benzyl-phospholium acenes.
Inorganic Chemistry, 2012Co-Authors: Yi Ren, Thomas BaumgartnerAbstract:A series of new phospholium acenes, quaternized with benzyl groups, was synthesized. Both different π-conjugated backbones and electron-donating/-withdrawing benzyl groups were systematically studied to reveal details on the nature of their structural dynamics. Extensive NMR studies (including variable concentration/temperature and 2D) suggested that the systems undergo intramolecular conformation changes in solution that are strongly affected by the electronic nature of the benzyl group, and thereby significantly affecting the Phosphole-typical σ*−π* interaction. This class of “smart” Phosphole system exhibits enhanced emission in the solid state and at low temperature in solution, due to aggregation-induced enhanced emission (AIEE). The dynamic features of these smart Phospholes also endow the systems with external-stimuli (thermal and mechanical force) responsive photophysical properties. Crystallographic studies and theoretical calculations confirmed that the thermal response of the phospholium system...
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external stimuli responsive photophysics and liquid crystal properties of self assembled Phosphole lipids
Journal of the American Chemical Society, 2011Co-Authors: Yi Ren, W H Kan, Matthew A Henderson, Paolo G Bomben, Curtis P Berlinguette, Thomas BaumgartnerAbstract:A series of new amphiphilic phosphonium materials that combine the electronic features of Phospholes with self-assembly features of lipids were synthesized. Variable concentration/temperature and 2D NMR studies suggested that the systems undergo intramolecular conformation changes between a “closed” and “open” form that are triggered by intermolecular interactions. The amphiphilic features of the phospholium species also induce liquid crystalline and soft crystal phase behavior in the solid state, which was studied by differential scanning calorimetry (DSC), polarized optical microscopy (POM), and variable temperature powder X-ray diffraction (VT-PXRD). The studies revealed that both conjugated backbones and counteranions work together to organize the systems into different morphologies (liquid crystal/soft crystal). Dithieno[3,2-b:2′,3′-d]Phosphole-based compounds exhibit enhanced emission in the solid state and at low temperature in solution due to aggregation-induced enhanced emission (AIEE). Photoindu...
Yoshihiro Matano - One of the best experts on this subject based on the ideXlab platform.
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Phosphole-Thiophene Hybrid: A Dual Role of Dithieno[3,4- b:3',4'- d]Phosphole as Electron Acceptor and Electron Donor.
The Journal of organic chemistry, 2018Co-Authors: Tomohiro Higashino, Yoshihiro Matano, Keiichi Ishida, Takaharu Satoh, Hiroshi ImahoriAbstract:We have synthesized dithieno[3,4-b:3′,4′-d]Phosphole derivatives as a new type of thiophene-fused Phospholes. These dithienoPhospholes were found to show intramolecular charge transfer interactions by introducing electron-donating or -withdrawing groups on the peripheral aryl groups. Namely, they exhibit the unique hybrid character of electron-withdrawing Phosphole and electron-donating thiophene.
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Phosphole–Thiophene Hybrid: A Dual Role of Dithieno[3,4‑b:3′,4′‑d]Phosphole as Electron Acceptor and Electron Donor
2018Co-Authors: Tomohiro Higashino, Yoshihiro Matano, Keiichi Ishida, Takaharu Satoh, Hiroshi ImahoriAbstract:We have synthesized dithieno[3,4-b:3′,4′-d]Phosphole derivatives as a new type of thiophene-fused Phospholes. These dithienoPhospholes were found to show intramolecular charge transfer interactions by introducing electron-donating or -withdrawing groups on the peripheral aryl groups. Namely, they exhibit the unique hybrid character of electron-withdrawing Phosphole and electron-donating thiophene
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Synthesis and Structure—Property Relationships of Phosphole-Based π Systems and Their Applications in Organic Solar Cells
ChemInform, 2015Co-Authors: Yoshihiro MatanoAbstract:Phosphole is a chemically tunable heterole, and its π-conjugated derivatives are potential candidates for optoelectronic materials. This account describes recent developments in the synthesis and structure-property relationships of π-conjugated Phosphole derivatives made by my research group. Thiophene-Phosphole-styrene, Phosphole-acetylene-arene, oligoPhosphole, polyPhosphole, areno[c]Phosphole, and Phosphole-heterole π systems are synthesized using titanacycle-mediated metathesis and palladium-catalyzed cross-coupling reactions. The structural, optical, and electrochemical properties of selected compounds are discussed. Initial results on some applications of thiophene-Phosphole copolymers, acenaphtho[c]Phospholes, and amine-terthiophene-Phosphole donor-π-acceptor dyes in organic solar cells are described. These results give valuable information and guidelines for designing new phosphorus-containing organic materials for molecular electronics.
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Comparison of 2-Arylnaphtho[2,3-b]Phospholes and 2-Arylbenzo[b]Phospholes: Effects of 2-Aryl Groups and Fused Arene Moieties on Their Optical and Photophysical Properties
Journal of Organic Chemistry, 2015Co-Authors: Yoshihiro Matano, Yuta Motegi, Shinsuke Kawatsu, Yoshifumi KimuraAbstract:Suzuki–Miyaura cross-coupling reactions were used in the divergent synthesis of a series of 2-arylnaphtho[2,3-b]Phosphole P-oxides and their benzo[b]Phosphole counterparts. We elucidated the electronic and steric effects of the 2-aryl groups and fused arene moieties on the optical and photophysical properties of these two types of Phosphole-based π-systems.
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Synthesis and Structure-Property Relationships of Phosphole-Based π Systems and Their Applications in Organic Solar Cells.
Chemical record (New York N.Y.), 2015Co-Authors: Yoshihiro MatanoAbstract:Phosphole is a chemically tunable heterole, and its π-conjugated derivatives are potential candidates for optoelectronic materials. This account describes recent developments in the synthesis and structure-property relationships of π-conjugated Phosphole derivatives made by my research group. Thiophene-Phosphole-styrene, Phosphole-acetylene-arene, oligoPhosphole, polyPhosphole, areno[c]Phosphole, and Phosphole-heterole π systems are synthesized using titanacycle-mediated metathesis and palladium-catalyzed cross-coupling reactions. The structural, optical, and electrochemical properties of selected compounds are discussed. Initial results on some applications of thiophene-Phosphole copolymers, acenaphtho[c]Phospholes, and amine-terthiophene-Phosphole donor-π-acceptor dyes in organic solar cells are described. These results give valuable information and guidelines for designing new phosphorus-containing organic materials for molecular electronics.
Régis Réau - One of the best experts on this subject based on the ideXlab platform.
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High variety of coordination modes of π-conjugated Phospholes in dinuclear rhenium carbonyls. Fluxional behavior of σ,π-complexes
Inorganica Chimica Acta, 2019Co-Authors: Yomaira Otero, Christophe Lescop, Muriel Hissler, Alejandro Arce, Deisy Peña, Régis RéauAbstract:A variety of dirhenium carbonyl complexes containing π-conjugated Phosphole derivatives were obtained from reaction of [Re2(CO)8(CH3CN)2] with each of the following Phospholes: 2,5-bis(2-thienyl)-1-phenylPhosphole (btpp), 2,5-bis(2-pyridyl)-1-phenylPhosphole (bpypp) and 1,2,5-triphenylPhosphole (tpp). The π-conjugated Phospholes were found to behave as two-, four- or six-electron donor ligands via σ or σ-π interactions with the metal centers, presenting bridging or chelating coordination modes as determined by spectroscopic methods and single crystal X-ray diffraction analysis. Metal-metal bond cleavage was evidenced when btpp was used, leading to a mono-substituted mononuclear complex. Variable-temperature 1H NMR studies for σ,π-complexes showed a fluxional behavior due to the restricted rotation around the P–C and C–C bonds of the 1,2,5-trisubstituted Phosphole ring.
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Bimetallic Gold(I) Complexes with Ethynyl-Helicene and Bis-Phosphole Ligands: Understanding the Role of Aurophilic Interactions in their Chiroptical Properties
Chemistry - A European Journal, 2016Co-Authors: Mehdi El sayed moussa, Jochen Autschbach, Hui Chen, Zuoyong Wang, Monika Srebro-hooper, Nicolas Vanthuyne, Soizic Chevance, Christian Roussel, J. A. Gareth Williams, Régis RéauAbstract:Monometallic gold(I)-alkynyl-helicene complexes (1a,b,) and bimetallic gold(I)-alkynyl-helicene architectures featuring the presence (2a,b) or absence (3a,b) of aurophillic intramolecular interactions were prepared by using different types of Phosphole ligands (mono-Phosphole L1 or bis-Phospholes L2,3). The influence of the Au(I) d10-metal center(s) on the electronic, photophysical and chiroptical properties of these unprecedented Phosphole-gold(I)-alkynyl-helicene complexes were examined. Experimental and theoretical results highlight the importance of ligand-to-ligand-type charge transfers and the strong effect of presence or absence of Au(I)-Au(I) interactions in 2a,b.
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Assembly of π-Conjugated Phosphole Azahelicene Derivatives into Chiral Coordination Complexes: An Experimental and Theoretical Study
Chemistry - A European Journal, 2010Co-Authors: Sebastien Graule, Jeanne Crassous, Jochen Autschbach, Mark Rudolph, Wenting Shen, J. A. Gareth William, Christophe Lescop, Régis RéauAbstract:Aza[n]helicene Phosphole derivatives have been prepared from aza[n]helicene diynes by the Fagan-Nugent route. Their photophysical properties (UV/Vis absorption and emission behavior) have been evaluated. Their behavior as P,N chelates towards coordination to PdII and CuI has been investigated: metal-bis(aza[n]helicene Phosphole) assemblies are formed by a highly stereoselective coordination process, as demonstrated by X-ray crystallography. An aza[6]helicene Phosphole bearing an enantiopure helicene part has been obtained, which allows the preparation of enantiopure PdII and CuI complexes with original topologies and high molar rotation (MR) and circular dichroism (CD). The structure-property relationship established from the experimental data has been studied in detail by theoretical studies (TDDFT calculations of UV/Vis, CD, and MR). Aza[n]helicene Phosphole derivatives show π conjugation extended over the entire molecule, and its influence on the MR of aza[6]helicene Phosphole 5 c has been demonstrated. Finally, it has been shown that the nature of the metal (coordination geometry and electronic interaction) can have a great impact on the amplitude of the chiroptical properties in metal-bis(aza[n]helicene Phosphole) assemblies.
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π-Conjugated Phosphole derivatives: synthesis, optoelectronic functions and coordination chemistry
Dalton transactions (Cambridge England : 2003), 2008Co-Authors: Jeanne Crassous, Régis RéauAbstract:π-Conjugated organophosphorus derivatives have recently emerged as valuable building blocks for the tailoring of functional molecular materials. We have focused for ten years on the synthesis of Phospholes bearing aromatic 2,5-substituents (phenyl, thienyl, pyridyl, etc.) and used these compounds as materials in fields as diverse as OLED's, WOLED's, non linear optics. Their properties (such as optical and electrochemical behaviour, thermal stability) can be finely tuned by functionalization at the P atom. Phosphole-based polymers have also been prepared by electropolymerization and have been used as sensors. More recently, Phospholes substituted by one or two pyridyl groups have proven to act as multidentate ligands with original coordination properties. A diversity of supramolecular rectangles that stacked into columns in the solid state has been obtained, opening new perspectives in the coordination-driven supramolecular organization of π-conjugated systems. Chiral π-conjugated Phospholes having a helical moiety have also been synthesized and spatially organized by using coordination to metallic ions, giving rise to sophisticated chiral complexes.
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π conjugated derivatives containing Phosphole rings synthesis properties and coordination chemistry
ChemInform, 2006Co-Authors: Muriel Hissler, Christophe Lescop, Régis RéauAbstract:La synthese et les proprietes de systemes π-conjugues lineaires incorporant des cycles Phospholes sont decrites. Des oligomeres a,a'-(Phosphole-aryl) de structures bien definies presentent de faibles ecarts HO-BV et leurs proprietes optiques et electrochimiques peuvent etre modulees a la suite de modifications chimiques impliquant l'atome de phosphore. Ces chromophores organophosphores π-conjugues peuvent s'associer a des ions metalliques pour former des complexes mono- ou dinucleaires. Les proprietes specifiques de ces complexes en font des materiaux attractifs pour les diodes electroluminescentes ainsi que pour des dispositifs actifs en optique non lineaire.
