Enantioselective chiral poly(thiophenes)

Lemaire, Marc; Delabouglise, Didier; Garreau, R.; Guy, Alain; Roncali, Jean

doi:10.1039/c39880000658

Cited by 155 publications

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“…In fact, the incorporation of chiral groups in polypyrroles and polythiophenes was reported. These groups confer original physico-chemical properties to the polymer [21][22][23]. Therefore, these optically active polymers were used to prepare chiral electrodes for asymmetric electrosynthesis, polarization-sensitive electro-optical devices, polarized photo-and electroluminescent devices and enantioselective sensors [24].…”

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New poly(p-phenylenevinylene) derivatives containing isosorbide unit in the side-chain

Zrida¹,

Hriz²,

Jaballah³

et al. 2014

Express Polym. Lett.

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Abstract. New conjugated PPV derivatives containing the chiral isosorbide group (P1-3) have been synthesized via the Gilch reaction. The polymers are optically active, soluble in common organic solvents and show good film-forming abilities. High number-average molecular weights were determined by size exclusion chromatography (SEC) (16·10 3 -21·10 3 g·mol -1 ). The molecular structures of the polymers were confirmed by nuclear magnetic resonance (NMR) and Fourier transform infrared (FTIR) spectroscopies. Thermogravimetric analysis of the polymers showed good thermal stability up to 320°C. The optical properties of these !-conjugated materials were investigated by UV-vis absorption and photoluminescence (PL) spectroscopies. The polymers show a yellow fluorescence in dilute solution, and an orange emission is observed in thin films. The introduction of the polar isosorbide groups improved the PL intensity, and quantum yields between 50 and 73% were obtained. The HOMO-LUMO energy levels were estimated by cyclic voltammetry, and the electrochemical gaps were 1.81, 1.83 and 2.48 eV for P1, P2 and P3, respectively. Single-layer diode devices were fabricated and show relatively low turn-on voltages between 3.1 and 3.4 V. Vol.8, No.10 (2014) 709-722 Available online at www.expresspolymlett.com DOI: 10.3144/expresspolymlett.2014.74 * Corresponding author, e-mail: mustapha.majdoub@fsm.rnu.tn © BME-PT insoluble in common organic solvents. This intractability has been addressed by chemically attaching aliphatic side-chains to the polymer backbone [19]. Hence, many PPV-type architectures are processed in a derivative form. The effects of the side-group structure on the opto-electronic properties have been extensively investigated [20]. However, most studies have involved nonpolar sidechains, and the effect of relatively polar side-groups was rarely reported (e.g PPV derivative containing ethylene oxide-type side chains) [12]. Here, we report the first PPV derivatives containing the polar and chiral isosorbide groups. In fact, the incorporation of chiral groups in polypyrroles and polythiophenes was reported. These groups confer original physico-chemical properties to the polymer [21][22][23]. Therefore, these optically active polymers were used to prepare chiral electrodes for asymmetric electrosynthesis, polarization-sensitive electro-optical devices, polarized photo-and electroluminescent devices and enantioselective sensors [24]. Herein, we present the synthesis and structural characterizations of the isosorbide-containing PPVs; the thermal, thin film surface, optical and electrochemical properties were investigated. Keywords: polymer synthesis, optically active polymers, semi-conducting polymers, isosorbide, photoluminescence eXPRESS Polymer Letters Experimental 2.1. Materials and measurementsThe poly (2-hexyloxy-5-methoxy-p-phenylenevinylene) (MH-PPV) was synthesized by using Gilch condensation. Detailed synthesis procedure can be found elsewhere [20].

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New poly(p-phenylenevinylene) derivatives containing isosorbide unit in the side-chain

Zrida¹,

Hriz²,

Jaballah³

et al. 2014

Express Polym. Lett.

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“…In particular, polythiophenes (PTs) (1)(2)(3)(4)(5)(6)(7)(8) with an optically active substituent in the 3 position have been studied for these purposes. These studies have been focused mainly on the chiral behavior of the PTs depending on solvent (solvatochromism) or temperature (thermochromism).…”

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Twisting macromolecular chains: Self-assembly of a chiral supermolecule from nonchiral polythiophene polyanions and random-coil synthetic peptides

Nilsson

Rydberg

Baltzer

et al. 2004

Proc. Natl. Acad. Sci. U.S.A.

102

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The self-assembly of a negatively charged conjugated polythiophene derivative and a positively charged synthetic peptide will create a chiral, well ordered supermolecule. This supermolecule has the three-dimensional ordered structure of a biomolecule and the electronic properties of a conjugated polymer. The molecular complex being formed clearly affects the conformation of the polymer backbone. A main-chain chirality, such as a predominantly one-handed helical structure induced by the acid-base complexation between the conjugated polymer and the synthetic peptide, is seen. The alteration of the polymer backbone influences the optical properties of the polymer, seen as changes in the absorption, emission, and Raman spectra of the polymer. The complexation of the polythiophene and the synthetic peptide also induce a change from random-coil to helical structure of the synthetic peptide. The supermolecule described in this article may be used in a wide range of applications such as biomolecular devices, artificial enzymes, and biosensors. T he development of chiral conjugated polymers (CPs) with a well defined structure is of great interest because of their potential for being used in optoelectronic devices, sensors, and catalysis. In particular, polythiophenes (PTs) (1-8) with an optically active substituent in the 3 position have been studied for these purposes. These studies have been focused mainly on the chiral behavior of the PTs depending on solvent (solvatochromism) or temperature (thermochromism). Chiral PTs normally exhibit optical activity in the -* transition. This phenomenon derives from the main-chain chirality when chains are aggregated to form a supramolecular, -stacked self-assembly due to intermolecular interactions in a poor solvent or at low temperature, whereas they show no activity in the UV-visible region in a good solvent or at high temperatures (5, 9-12). Recent studies (13-16), using optically inactive CPs that become chiral after addition of a chiral guest, show that chirality introduction can also be a result of a main-chain chirality, such as a predominantly one-handed helical structure induced by a acidbase complexation between the CP and the chiral guest.Natural biopolymers such as protein and DNA frequently have helical conformations that contribute to the three-dimensional ordered structure and the specific function of the biopolymer. As a part of the cell signaling pathways and enzymatic reactions, conformational alterations of biomolecules are very important in biological systems. Likewise do the conformational alterations of CPs allow direct connection between the geometry of chains and the resulting electronic structure and optical processes. Hence, it would be of great interest to combine helical biomolecules and optically inactive PTs. Such combinations have been reported (17,18), and an induced chirality in the PTs due to the helical biomolecules was detected. To make a hybrid supermolecule between an optically inactive PT and a biomolecule with a random-coil conformation is ...

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“…A diferença observada na velocidade de oxidação (velocidade de inserção do agente dopante quiral na matriz polimérica quiral) é causado pelo reconhecimento estereosseletivo durante o ciclo redox. Este pode ser considerado o primeiro exemplo de avaliação amperométri-ca de enantiosseletividade (esquema 8) 60 . Uma primeira reação eletródica de diferenciação enantiomérica foi registrada por Komori e Nonaka (esquema 9) 61 e seguido por uma série de importantes resoluções 13 .…”

Section: Iii: Uso De Eletrodos Modificadosunclassified

Estereosseletividade em reações eletródicas

Azevedo¹,

Goulart²

1997

Quím. Nova

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Recebido em 15/12/95; aceito em 11/12/96 STEREOSELECTIVITY IN ELECTRODIC REACTIONS. This review discusses the present state of the art of the stereochemistry of electrochemical reactions. The extent of asymmetric induction is progressing, but in general diastereoselectivities and enantioselectivities remain behind those from chemical synthesis. In recent years, new methodological developments have been successful. Effects that play important roles in homogeneous chemistry have been used with success. Lack of expressive enantiomeric excess (ee) could be related to the absence of tightly organized structures during the reaction of interest. The highest ee might be expected for redox reactions where conformational preference in transition state plays the important role or for the ones performed while adsorbed on the electrode, and where the chiral element is also at the surface, either adsorbed or chemically bound to the surface and interacting directly with the substrate. Electroenzymatic synthesis has a promising future.Keywords: asymmetric electrosynthesis; chiral auxiliaries; chiral electrodes. REVISÃO INTRODUÇÃOUma reação eletródica é uma reação de oxirredução heterogênea que ocorre em uma interface formada por um eletrodo (fase condutora eletrônica) e por espécies (fase condutora iônica e espécies eletroativas) imediatamente adjacentes à superfície em dimensões moleculares. A espécie eletroativa, neutra ou carregada, está normalmente em solução, mas, gases e sólidos são também passíveis de sofrerem reações nestas condições. Eletrodos podem ser considerados como molé-culas de dimensões gigantescas cuja habilidade em fornecer ou aceitar elétrons pode ser ajustada pelo controle fino do potencial do eletrodo.Um grande número de transformações químicas via eletroquímica tem sido demonstrada, tanto ao nível industrial 1 como em escala laboratorial e vários textos atuais tratam da importância da eletroquímica em síntese orgânica [2][3][4][5][6][7][8][9][10] . Uma das principais metas dos eletroquímicos orgânicos é realizar eletrossínteses eficientes, com alto rendimento em produtos e em eficiência de corrente, em processos reconhecidamente menos poluentes, mais rápidos, suaves e mais baratos. Muitos processos com estas características são conhecidos, com aplicação industrial 1 . Existem exemplos de reações cuja realização só é possível via eletroquímica [1][2][3]11 . Deve ser inicialmente reconhecido que a ativação eletroquímica constitui um método não térmico poderoso de geração de intermediários reativos, com obtenção de alta concentração local das espécies eletrogeradas 2 . O objetivo do presente artigo restringe-se, porém, à discussão dos aspectos ligados à estereosseletividade das eletrólises, registrando seus aspectos mais importantes, sem pretensões a ser exaustivo. Deve ser enfatizado que, em todas as reações descritas, a etapa eletroquímica constitui ou a etapa de diferenciação estereoquímica ou é fundamental ao resultado reacional. Na maioria do esquemas, as reações citadas são as de melhores rendimentos e...

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Enantioselective chiral poly(thiophenes)

Abstract: Chiral poly(thiophenes) have been synthesized by electropolymerization; they exhibit high specific rotation, stability, and conductivity and can stereoselectively recognize chiral anions used as doping agents during voltammetric cycles.

Cited by 155 publications

References 1 publication

New poly(p-phenylenevinylene) derivatives containing isosorbide unit in the side-chain

New poly(p-phenylenevinylene) derivatives containing isosorbide unit in the side-chain

Twisting macromolecular chains: Self-assembly of a chiral supermolecule from nonchiral polythiophene polyanions and random-coil synthetic peptides

Estereosseletividade em reações eletródicas

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