Towards chiral metals. Synthesis of chiral conducting polymers from optically active thiophene and pyrrole derivatives

Kotkar, Dilip; Joshi, Vishwas N.; Ghosh, Pushpito K.

doi:10.1039/c39880000917

Cited by 78 publications

(39 citation statements)

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“…The latter combine high electrical conductivity, with thermal and environmental stability. [17][18][19][20][21][22][23][24][25][26][27][28][29] In the last few years donor substituted tricyanovinyl compounds have received a lot of interest. Due to their strong solvatochromic properties, which mainly originate from their donoracceptor substitution, they can be used as model compounds for dyes with strong NLO properties.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of tricyanovinyl-substituted thienylpyrroles and characterization of the solvatochromic, electrochemical and non-linear optical properties

et al. 2005

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-Tricyanovinyl-substituted 1-(alkyl)aryl-2-(2´-thienyl)pyrroles 1 have been synthesized by direct tricyanovinylation reaction of 1-(alkyl)aryl-2-(2´-thienyl)pyrroles 2 using TCNE. The tricyanovinyl-derivatives 1 display dramatic reductions in both their optical and electrochemical band gaps relative to thienylpyrrole precursors 2. The solvatochromic behavior of compounds 1 was investigated in a variety of solvents. Hyper-Rayleigh scattering was used to measure the first hyperpolarizabilities β of the mentioned compounds. The β values show that the new compounds prepared could be used on the manufacture of materials with good non-linear (NLO) properties.

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Section: Introductionmentioning

confidence: 99%

Synthesis of tricyanovinyl-substituted thienylpyrroles and characterization of the solvatochromic, electrochemical and non-linear optical properties

et al. 2005

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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].…”

mentioning

confidence: 99%

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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“…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).…”

mentioning

confidence: 99%

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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Towards chiral metals. Synthesis of chiral conducting polymers from optically active thiophene and pyrrole derivatives

Cited by 78 publications

References 1 publication

Synthesis of tricyanovinyl-substituted thienylpyrroles and characterization of the solvatochromic, electrochemical and non-linear optical properties

Synthesis of tricyanovinyl-substituted thienylpyrroles and characterization of the solvatochromic, electrochemical and non-linear optical properties

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

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