Asymmetrically substituted distyrylbenzenes and their polar crystal structures

Collas, Alain; Borger, Roeland De; Amanova, Tatyana; Velde, Christophe M. L. Vande; Baeke, Jan K.; Dommisse, Roger; Alsenoy, C. Van; Blockhuys, Frank

doi:10.1039/c0nj00732c

Cited by 5 publications

(3 citation statements)

References 40 publications

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“…Within the class of oligomeric or low-molecular-weight organic semiconductors distyrylbenzenes (DSBs)-oligomers of poly(p-phenylene vinylene) or PPV and their derivatives enjoy a great deal of interest as new materials for opto-electronic applications such as organic lightemitting diodes (OLEDs) [1][2][3][4][5][6][7], gas-and ion-selective sensors [8,9,10,11], organic memories, and nonlinear optics (NLO) [12]. In a number of these applications, the oligomers need to be in their electrically conducting state (the neutral compounds are electrical insulators) and this can be easily achieved by oxidizing or reducing them using either a chemical or an electrochemical procedure; the latter has the advantage that the active material can be electro-deposited from a standard electrochemical cell directly onto a pre-chosen substrate.…”

Section: Introductionmentioning

confidence: 99%

Quantum chemical study of self-doping PPV oligomers: spin distribution of the radical forms

et al. 2012

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A quantum chemical study was performed on ten different self-doping PPV oligomers. The geometry and the different weak intramolecular interactions were studied. The atomic spin populations were calculated using the FOHI method and related to the calculated EPR parameters. The effects of the removal of methoxy groups, the introduction of nitrogen atoms, and the relocation of the self-doping sidechain on the geometry, the spin distribution, and the EPR parameters have been described.

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Section: Introductionmentioning

confidence: 99%

Quantum chemical study of self-doping PPV oligomers: spin distribution of the radical forms

et al. 2012

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“…Indeed, the direct oligomeric descendants of PPV, i.e., distyrylbenzene and its derivatives, have been applied as the opto-and electro-active components in OLEDs [10][11][12][13][14][15][16] and in gas-and ion-selective sensors, 17,18 and they display properties which may well find application in organic memories and non-linear optics (NLO). [19][20][21] While neutral oligomers are insulators, they can readily be converted to radical cations by chemical 22,23 or electrochemical 24 oxidation. Chemical doping can be easily achieved by exposure to I 2 , a method also commonly used to generate radical cations or polaron states in polymers.…”

Section: Introductionmentioning

confidence: 99%

The solid-state organization of ‘self-doped’ PPV oligomers

Ling

Kozakiewicz

Blockhuys

et al. 2011

Phys. Chem. Chem. Phys.

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Using a combination of multi-frequency EPR and NMR spectroscopy and quantum-chemical calculations at the level of Density Functional Theory (DFT), the organization of self-doped PPV oligomers in their solid state is investigated. The analysis of the different spectra shows that the electrochemical procedure used to self-dope these materials produces positive radicals (polarons) in an almost quantitative way, but still magnetically isolated polarons are observed. The difference between chemical and electrochemical oxidation of the oligomers is studied in detail. Furthermore, ageing of the electrochemically oxidized oligomers may be accompanied by a stacking of the oligomers.

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“…Polynitrostilbenes, such as 2,2 ′ ,4,4 ′ ,6,6 ′ -hexanitrostilbene (HNS) [1][2][3] are well known explosives with excellent thermal stability and detonation properties. Nitrostilbene-based compounds are also widely used as organic nonlinear optical materials [4][5][6][7][8][9] for high-performance electro-optical devices. The Mizoroki-Heck reaction, Negishi-Stille coupling and Wittig-type reactions have proved to be quite versatile in the preparation of different substituted stilbenes.…”

mentioning

confidence: 99%

Synthesis of Polynitrostilbenes from 2,4,6-Trinitro-M-Xylene and 2,4,6-Trinitrotoluene by a Microwave-Assisted Solvent Free Method

Wei

et al. 2014

Journal of Chemical Research

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A microwave-assisted method for the synthesis of polynitrostilbenes involving the condensation of 2,4,6-trinitro-m-xylene and 2,4,6-trinitrotoluene with aryl aldehydes in the presence of piperidine and silica-gel is reported. Compared with conventional methods, a shorter reaction time is required and this method has a lower environmental impact. A mechanism for the reaction is also proposed and supported by UV-Vis absorption spectroscopy.Polynitrostilbenes, such as 2,2 ′ ,4,4 ′ ,6,6 ′ -hexanitrostilbene (HNS) 1-3 are well known explosives with excellent thermal stability and detonation properties. Nitrostilbene-based compounds are also widely used as organic nonlinear optical materials 4-9 for high-performance electro-optical devices. The Mizoroki-Heck reaction, Negishi-Stille coupling and Wittig-type reactions have proved to be quite versatile in the preparation of different substituted stilbenes. However, they need transition-metal catalysis and complicated sequences to form halogen-and phosphorus-containing substrates. [10][11][12][13][14][15] More recently, transition metal catalysts especially palladium have been widely studied in stilbene syntheses. Other methods include the McMurry coupling and alkene cross-metathesis as well as one-pot multicatalytic processes. [16][17][18][19] These sometimes lacked stereoselectivity and the cost was increased by using noble metals. We have reported 20 that 2,4,6-trinitro-m-xylene (TNMX) will condense with two equivalents of aromatic aldehydes in boiling benzene with a piperidine catalyst. The whole process was time-consuming but proceeded with high stereoselectivity.Recently, microwave-assisted organic synthesis (MAOS) has developed into a popular branch of synthetic organic chemistry, 21-25 as it helps in minimising the energy consumption required for heating as well as the time required for the reaction. However, a combination of microwave and solvent-free conditions are rare in polynitrostilbene chemistry. We now report a useful and solvent-free method for the synthesis of an array polynitrostilbenes based on TNMX and 2,4,6-trinitrotoluene (TNT) with piperidine catalysis utilising microwave irradiation. To make the system safer, silica-gel was used as an effective solid support. In order to shed more light on this reaction, the mechanism of the reaction was also studied by UV-Vis absorption.

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Asymmetrically substituted distyrylbenzenes and their polar crystal structures

Cited by 5 publications

References 40 publications

Quantum chemical study of self-doping PPV oligomers: spin distribution of the radical forms

Quantum chemical study of self-doping PPV oligomers: spin distribution of the radical forms

The solid-state organization of ‘self-doped’ PPV oligomers

Synthesis of Polynitrostilbenes from 2,4,6-Trinitro-M-Xylene and 2,4,6-Trinitrotoluene by a Microwave-Assisted Solvent Free Method

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