New mechanistic aspects on the formation of poly(isothianaphthene) from P 4 S 10 and phthalic anhydride derivatives: carbon–carbon bond formation and cleavage via a cyclic reaction mechanism

Paulussen, Harald; Haitjema, Hj; Asselt, R. van; Mylle, P; Adriaensens, Peter; Gelan, Jan; Vanderzande, Dirk

doi:10.1016/s0032-3861(99)00537-6

Cited by 11 publications

(10 citation statements)

References 14 publications

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“…In the last decade, there has also been extensive work on the development of a straightforward chemical polymerization route toward PITN, in which various isothianaphthene derivatives are utilized 7–11. Although important progress has been achieved in the methods of PITN preparation and in the exploration of the mechanistic aspects of its structure and formation,12, 13 the practical applications of this polymer are still limited. This is due to the poor processability, insolubility, and infusibility of PITN.…”

Section: Introductionmentioning

confidence: 99%

Convenient synthesis and polymerization of 5,6‐disubstituted dithiophthalides toward soluble poly(isothianaphthene): An initial spectroscopic characterization of the resulting low‐band‐gap polymers

Polec

Henckens

Goris

et al. 2003

J. Polym. Sci. A Polym. Chem.

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A new synthetic procedure toward substituted dithiophthalides, 5,6-dialkyloxydithiophthalide and 5,6-dithioalkyldithiophthalide, is presented. 5,6-Dithiooctyldithiophthalide was obtained from 4,5-dichlorophthalic acid in an eight-step reaction with an overall yield of 26%. 5,6-Dioctyloxydithiophthalide was obtained from 4,5dihydroxyphthalic acid dimethyl ester in a seven-step reaction (overall yield ϭ 15%). Both monomers were polymerized by a thermal and nonoxidative polymerization that resulted in soluble poly(isothianaphthene) derivatives with a band gap of about 1.2 eV. Photoinduced absorption measurements revealed the existence of charged excitations upon illumination. The photoinduced charge generation, combined with the extensive light-harvesting properties and the easy processability, makes these materials quite promising for photovoltaic applications.

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Section: Introductionmentioning

confidence: 99%

Convenient synthesis and polymerization of 5,6‐disubstituted dithiophthalides toward soluble poly(isothianaphthene): An initial spectroscopic characterization of the resulting low‐band‐gap polymers

Polec

Henckens

Goris

et al. 2003

J. Polym. Sci. A Polym. Chem.

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“…All of the major infrared bands characteristic of PITN were observed in all the film spectra and the band positions were consistent with those published in the literature. 19,20,38,39,41,69 Peak intensity increases for all of the peaks as the deposition temperature increases. For the film deposited at 130 °C, peaks appear at 737, 847, 874, 976, 1055, 1142, 1188, 1221, 1265, 1381, 1452, 1589, and 1680 cm −1 .…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…Concentrated H 2 SO 4 will react directly with both isothianaphthene ( 3 ) and 1,3-dihydrobenzo[c] thiophene 2-oxide ( 2 ) to form PITN ( 5 ) . Phthalic anhydride has been shown to react with thionating reagents, such as phosphorus pentasulphide (P 4 S 10 ), to yield PITN. , More promisingly, the molecule 1,3-dihydroisothianaphthene (DHITN) ( 1 ), which unlike 3 is stable, will react with FeCl 3 , N-chlorosuccinimide, and other species to produce PITN (route III in Scheme ). − This provides a much shorter and more direct synthesis route to PITN. However, the chemical reaction of any of these monomers in solution will only result in PITN powder instead of a film.…”

Section: Introductionmentioning

confidence: 99%

“…19 Phthalic anhydride has been shown to react with thionating reagents, such as phosphorus pentasulphide (P 4 S 10 ), to yield PITN. 38,39 More promisingly, the molecule 1,3-dihydroisothianaphthene (DHITN) (1), which unlike 3 is stable, will react with FeCl 3 , N-chlorosuccinimide, and other species to produce PITN (route III in Scheme 1). 40−42 This provides a much shorter and more direct synthesis route to PITN.…”

Section: ■ Introductionmentioning

confidence: 99%

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Tunable Low Bandgap Polyisothianaphthene via Oxidative Chemical Vapor Deposition

Borrelli

Gleason

2013

Macromolecules

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Despite polyisothianaphthene's (PITN) desirable properties, complex synthetic routes and lack of solubility have limited its utility, particularly when thin films are required. Here, we report a one-step process for the simultaneous synthesis and film deposition of unsubstituted PITN using oxidative chemical vapor deposition (oCVD). The PITN film properties were easily tuned by controlling the substrate temperature over a range from 70 to 130 °C during the oCVD process. The positions of the absorption maxima in the UV−vis−NIR absorption spectra were considerably redshifted by over 100 nm with increasing deposition temperature. This resulted in a decrease in the bandgap from 1.14 to 1.05 eV. Downshifts in many peak positions were observed in the Fourier transform infrared (FTIR) and Raman spectra with increasing deposition temperature. These observations suggest longer polymer conjugation lengths were achieved with increasing deposition temperature.

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“…A possible mechanism includes the formation of an endoperoxide upon reaction of the IBF and oxygen, which in turn rearranges into to a diketone followed by conversion of the diketone to the dithioketone with Lawesson’s reagent and cyclization to form the ITN . In the case of 8c , the dicyanovinyl group was cleaved during the procedure, presumably to a thioaldehyde by Lawesson’s reagent, and thus treatment with excess malonitrile and base was necessary to obtain 10c . Dye 10d was deprotected under acid conditions in a similar manner as 8d .…”

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confidence: 99%

Near-Infrared Fluorophores Containing Benzo[c]heterocycle Subunits

2008

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The syntheses and spectroscopic properties of eight new push-pull type near-infrared fluorophores that contain either isobenzofuran or isothianapthene subunits are presented. The isobenzofuran dyes demonstrate significantly red-shifted absorption from their isothianaphthene counterparts, which is attributed to isobenzofuran's more potent pro-quinoidal character.In vivo near-infrared (NIR) fluorescence imaging is rapidly emerging as a powerful diagnostic method. 1 In the NIR region (650-900nm) biological chromophores exhibit low absorption and autofluorescence 2 thus allowing photons to pass through the tissue and rendering this technique relatively non-invasive. With applications such as vascular mapping of the heart 3 and brain 4 and visualization of various pathologies including tumors 5 , atherosclerosis 6 , and β-amyloid plaques 7 , the demand for new NIR fluorescent contrast agents is ever increasing.Our group resently reported the synthesis and in vivo imaging properties of NIAD-4 (1), NIM-1 (2), and NIM-2 (3), all donor-acceptor type dyes. 7a,8 In the case of 2 and 3, it was found that the incorporation of benzo [c] Isothianapthene has a relatively long history as a component in functional materials, with examples in fluorophores, 9 OLEDs, 10 photovoltaics, 11 and low band-gap polmyers, of which polyisothianaphthene (PITN) 12 is the progenitor. The smaller band-gap of these ITN containing materials over similar thiophene containing materials is a result of the increased contribution of the quinoid resonance structure (Figure 2) due to the stabilization achieved by aromatization of the benzene ring. 13 In contrast, only a few examples 14 of functional materials containing isobenzofuran are reported in the literature, presumably due its reduced stability. 15 For this reason, we predicted that IBF would prove even more pro-quinoidal and that its incorporation into donor-acceptor dyes would further reduce the band-gap of these materials.In order to test this principal, we synthesized a series of IBF and ITN dyes similar to NIAD-4 (Scheme 1). Four different electron donating (R) groups, H-, MeO-, HO-, and Me 2 N-, were incorporated in order to span a range of wavelengths. Appropriately substituted aryl-lactones 5a-d were either purchased or synthesized via acid mediated condensation 16 of 2-carboxybenzaldehyde and substituted benzenes. In the case of the phenol group (R = OH), TiPS protection was employed. Initially, the IBF framework was constructed with a free 5 position on the thiophene, which was subsequently lithiated and the formylated with DMF. However, these unsubstituted intermediate compounds proved relatively difficult to isolate and purify, resulting in poor yields for the formylation.Exploiting the acetal protected aldehydes allowed us to bypass these troublesome intermediates. Protected aldehydes 7a-d were produced in one step by reaction of the lactones with the lithio-derivative of 6 17 followed by dehydration with acetic anhydride and deprotection with aqueous acetic acid. Knoevenega...

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New mechanistic aspects on the formation of poly(isothianaphthene) from P 4 S 10 and phthalic anhydride derivatives: carbon–carbon bond formation and cleavage via a cyclic reaction mechanism

Cited by 11 publications

References 14 publications

Convenient synthesis and polymerization of 5,6‐disubstituted dithiophthalides toward soluble poly(isothianaphthene): An initial spectroscopic characterization of the resulting low‐band‐gap polymers

Convenient synthesis and polymerization of 5,6‐disubstituted dithiophthalides toward soluble poly(isothianaphthene): An initial spectroscopic characterization of the resulting low‐band‐gap polymers

Tunable Low Bandgap Polyisothianaphthene via Oxidative Chemical Vapor Deposition

Near-Infrared Fluorophores Containing Benzo[c]heterocycle Subunits

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