Synthesis of novel 1,3-bis(5-diarylaminothiophen-2-yl)isothianaphthenes

Kisselev, Roman; Thelakkat, Mukundan

doi:10.1039/b202943j

Cited by 27 publications

(21 citation statements)

References 22 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Diphenylamine has been coupled with 2‐halothiophenes, in the presence of a palladium source (Pd(OAc) 2 26, 27 or [Pd 2 dba 3 ] {dba=dibenzylideneacetone}26) in conjunction with P t Bu 3 (36–78 % from 2‐bromothiophene26–28), or by use of CuI‐mediated modified Ulmann conditions (40 % yield from 2‐iodothiophene) 29. Various other diarylamines including bis(4‐alkoxyphenyl)amines have been coupled with α,α′‐dibromooligothiophenes and with 1,3‐bis(5‐bromothien‐2‐yl)benzo[ c ]thiophene in moderate yields in the presence either of Pd(OAc) 2 /P t Bu 3 30 or of [Pd(dppf)Cl 2 ]/dppf {dppf=1,1′‐bis(diphenylphosphino)ferrocene}31 as catalysts.…”

Section: Resultsmentioning

confidence: 99%

Bis[bis‐(4‐alkoxyphenyl)amino] Derivatives of Dithienylethene, Bithiophene, Dithienothiophene and Dithienopyrrole: Palladium‐Catalysed Synthesis and Highly Delocalised Radical Cations

Odom

Lancaster

Beverina

et al. 2007

Chemistry A European J

116

View full text Add to dashboard Cite

Five diamines with thiophene-based bridges--(E)-1,2-bis{5-[bis(4-butoxyphenyl)amino]-2-thienyl}ethylene (1), 5,5'-bis[bis(4-methoxyphenyl)amino]-2,2'-bithiophene (2), 2,6-bis[bis(4-butoxyphenyl)amino]dithieno[3,2-b:2',3'-d]thiophene (3), N-(4-tert-butylphenyl)-2,6-bis[bis(4-methoxyphenyl)amino]dithieno[3,2-b:2',3'-d]pyrrole (4 a) and N-tert-butyl-2,6-bis[bis(4-methoxyphenyl)amino]dithieno[3,2-b:2',3'-d]pyrrole (4 b)--have been synthesised. The syntheses make use of the palladium(0)-catalysed coupling of brominated thiophene species with diarylamines, in some cases accelerated by microwave irradiation. The molecules all undergo facile oxidation, 4 b being the most readily oxidised at about -0.4 V versus ferrocenium/ferrocene, and solutions of the corresponding radical cations were generated by addition of tris(4-bromophenyl)aminium hexachloroantimonate to the neutral species. The near-IR spectra of the radical cations show absorptions characteristic of symmetrical delocalised species (that is, class III mixed-valence species); analysis of these absorptions in the framework of Hush theory indicates strong coupling between the two amine redox centres, stronger than that observed in species with phenylene-based bridging groups of comparable length. The strong coupling can be attributed to high-lying orbitals of the thiophene-based bridging units. ESR spectroscopy indicates that the coupling constant to the amino nitrogen atoms is somewhat reduced relative to that in a stilbene-bridged analogue. The neutral species and the corresponding radical cations have been studied with the aid of density functional theory and time-dependent density functional theory. The DFT-calculated ESR parameters are in good agreement with experiment, while calculated spin densities suggest increased bridge character to the oxidation in these species relative to that in comparable species with phenylene-based bridges.

show abstract

Section: Resultsmentioning

confidence: 99%

Bis[bis‐(4‐alkoxyphenyl)amino] Derivatives of Dithienylethene, Bithiophene, Dithienothiophene and Dithienopyrrole: Palladium‐Catalysed Synthesis and Highly Delocalised Radical Cations

Odom

Lancaster

Beverina

et al. 2007

Chemistry A European J

116

View full text Add to dashboard Cite

show abstract

“…The BMA-nT series has been modified to show electronic absorption in the visible wavelength region by the replacement of the thiophene unit with a isothianaphthene group. 165 A p-n heterojunction photovoltaic device consisting of a triarylphthalocyanine-based amorphous molecular material, PcArA (M: TiLO), as a p-type semiconductor and N,N9-dimethyl-3,4,9,10-perylenebis(dicarboximide) (MPCI) as an n-type semiconductor exhibited PV properties when irradiated with 400-600 nm light which MPCI absorbs. The action spectrum resembled the electronic absorption spectrum of MPCI.…”

Section: -4 Emitting Amorphous Molecular Materialsmentioning

confidence: 99%

Photo- and electroactive amorphous molecular materials—molecular design, syntheses, reactions, properties, and applications

2005

View full text Add to dashboard Cite

A new field of organic materials science that deals with amorphous molecular glasses has been opened up. In addition, amorphous molecular materials have constituted a new class of functional organic materials for use in various applications. This article is focused on the recent progress of studies on photo-and electroactive amorphous molecular materials, highlighting photochromic amorphous molecular materials, amorphous molecular resists, and amorphous molecular materials for use in devices such as organic EL devices. The molecular design concepts, syntheses, reactions, molecular and solid-state properties, functions, and device fabrication and performance are described.

show abstract

“…7 It has been revealed that polybenzo [c]thiophenes possess unique optical properties originating from their narrow HOMO−LUMO energy gaps over the past few decades. 8 More recently, functionalized benzo [c]thiophene monomers were also synthesized aiming to their use in solar cells, 9 electroluminescence devices, 10 and so on. 11 A general method for benzo [c]thiophene synthesis is the ring closure of the corresponding ortho-dicarbonyl benzene derivatives by treating with Lawesson's reagent (Scheme 1a).…”

Section: ■ Introductionmentioning

confidence: 99%

Synthesis of Benzo[c]thiophenes by Rhodium(III)-Catalyzed Dehydrogenative Annulation

Fukuzumi¹,

Unoh²,

Nishii³

et al. 2016

J. Org. Chem.

View full text Add to dashboard Cite

show abstract

Synthesis of novel 1,3-bis(5-diarylaminothiophen-2-yl)isothianaphthenes

Abstract: We report the synthesis, electrochemical and optical properties of novel 1,3-bis(5-diarylaminothiophen-2-yl)isothianaphthenes obtained by palladium-catalysed amination of 1,3-bis(5-bromothiophen-2-yl)isothianaphthene with diarylamines.

Cited by 27 publications

References 22 publications

Bis[bis‐(4‐alkoxyphenyl)amino] Derivatives of Dithienylethene, Bithiophene, Dithienothiophene and Dithienopyrrole: Palladium‐Catalysed Synthesis and Highly Delocalised Radical Cations

Bis[bis‐(4‐alkoxyphenyl)amino] Derivatives of Dithienylethene, Bithiophene, Dithienothiophene and Dithienopyrrole: Palladium‐Catalysed Synthesis and Highly Delocalised Radical Cations

Photo- and electroactive amorphous molecular materials—molecular design, syntheses, reactions, properties, and applications

Synthesis of Benzo[c]thiophenes by Rhodium(III)-Catalyzed Dehydrogenative Annulation

Contact Info

Product

Resources

About