Novel Extended Tetrathiafulvalenes Based on Acetylenic Spacers: Synthesis and Electronic Properties

Nielsen, Mogens Brøndsted; Utesch, Nils F.; Moonen, Nicolle N. P.; Boudon, Corinne; Gisselbrecht, Jean‐Paul; Concilio, Simona; Piotto, Stefano; Seiler, Paul; Günter, Peter; Gross, Maurice; Diederich, François

doi:10.1002/1521-3765(20020816)8:16<3601::aid-chem3601>3.0.co;2-n

Cited by 67 publications

(35 citation statements)

References 21 publications

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“…For example, compared to a dodec‐1,11‐diene‐3,5,7,9‐tetrayne, which exhibits its longest wavelength absorption maximum at 405 nm,25 the substitution of the two terminal carbon atoms by phosphorus, as in 7 , leads to a bathochromic shift of the lowest energy absorption maximum of 80 nm, which corresponds to a difference in HOMO–LUMO gap between the two compounds of 0.50 eV. The doping strength of the two phosphaalkenes in 7 is similar to that of two dithiafulvenes that, when implemented at the termini of octatetraynes, result in a shift of the respective absorption maximum to 484 nm 26. This wavelength is similar to that for the corresponding absorption of compound 7 .…”

Section: Methodsmentioning

confidence: 97%

Incorporating Phosphaalkenes into Oligoacetylenes

et al. 2008

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Eine Verkleinerung der HOMO‐LUMO‐Bandlücke um 0.5 eV wird beobachtet, wenn die beiden terminalen Kohlenstoffatome eines Tetrain‐verknüpften Bisalkens durch zwei Phosphorzentren ersetzt werden. Die acetylenischen Phosphaalkene sind aus einem ambivalenten Carben‐artigen C5‐Intermediat zugänglich und eignen sich für den Aufbau komplexer phosphor‐ und kohlenstoffreicher Moleküle (siehe Bild; C grau, P violett).

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Section: Methodsmentioning

confidence: 97%

Incorporating Phosphaalkenes into Oligoacetylenes

et al. 2008

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“…Each of these rings is characterized by a nucleus independent chemical shift index of NICS(1) zz = -23.96 ppm, and the rings are according to this parameter slightly less aromatic than the parent 1,3-dithiolium for which NICS(1) zz = -28.35 ppm [23]. Efficient synthetic protocols for preparing the acetylenic DTF and TTF derivatives 6 [24,25] and 7 [26] have been developed. These compounds are convenient building blocks for incorporating DTF and TTF into DHAs using transitionmetal-catalyzed cross-coupling reactions.…”

Section: Figmentioning

confidence: 99%

“…TTF undergoes two reversible one-electron oxidations. Both the DTF and TTF can be functionalized with an acetylenic unit, and the resulting compounds (6 and 7) can be used as building blocks for acetylenic scaffolding[24][25][26].…”

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confidence: 99%

New routes to functionalized dihydroazulene photoswitches

Nielsen

Broman

Petersen

et al. 2010

Pure and Applied Chemistry

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Molecular photoswiches are important for the development of advanced materials and molecular electronics devices. The dihydroazulene (DHA) is a particularly attractive molecule as it undergoes a light-induced ring opening to a vinylheptafulvene (VHF) isomer with altered optical properties. While functionalization of the five-membered ring of DHA has been possible for the last 25 years, this was not the case for the seven-membered ring. This article summarizes our synthetic efforts in achieving this goal. Incorporation of an alkyne at C-7 was accomplished by (i) regioselective bromination of DHA, followed by (ii) elimination of HBr, and (iii) Pd-catalyzed cross-coupling with triisopropylsilylacetylene. Light-induced ring opening of this DHA followed by thermal ring closure provided a mixture of 6-and 7-substituted DHAs with different absorption characteristics. The isomer ratio was controlled by the wavelength of irradiation and the solvent polarity. The dibromide formed in the initial step served as a precursor for a 3-bromo-functionalized azulene that was employed as a building block for acetylenic scaffolding. Incorporation of a dithiafulvene (DTF) unit at the five-membered ring of DHA resulted in a significant red-shift in the longest-wavelength absorption and consequently a lowering of the energy required for ring opening. Incorporation of a redox-active tetrathiafulvalene (TTF) unit allowed for redox-controlled photoswitching.Scheme 4 Synthesis of functionalized azulenes starting from the dibromide 8.Scheme 5 Incorporation of redox-active DTF and TTF units.

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“…Acetylenic scaffolding starting from ethynylated TTF derivatives afforded extended conjugated materials with promising optoelectronic properties [58,62]. We prepared the new tris(tetrathiafulvaleno)dodecadehydro [18]annulene 14, bearing six peripheral n-hexyl substituents, by oxidative Glaser-Hay cyclization of diethynylated TTF, obtained by deprotection of precursor 15 ( Fig.…”

Section: Nonaggregating Tris(tetrathiafulvaleno)dodecadehydro[18]annumentioning

confidence: 99%

Conjugation and optoelectronic properties of acetylenic scaffolds and charge-transfer chromophores

Kivala

Diederich

2008

Pure and Applied Chemistry

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Our group started a research program in acetylene chemistry in 1987; since then, an intense research effort led to a fascinating journey into acetylenic scaffolding, aimed at exploring conjugative and optoelectronic properties of acetylenic chromophores. This journey included the generation of a unique molecular construction kit for acetylenic scaffolding, consisting of (E)-1,2-diethynylethenes [DEEs, (E)-hex-3-ene-1,5-diynes], tetraethynylethenes (TEEs, 3,4-diethynylhex-3-ene-1,5-diynes), chiral 1,3-diethynylallenes (DEAs, hepta-3,4-diene-1,6-diynes), 1,4-di and 1,1,4,4-tetraethynylbutatrienes, chiral trialkynylmethanes, and 1,1,2,2-tetraethynylethanes. These building modules were subsequently applied to the synthesis of carbon-rich architectures extending into one, two, and three dimensions. They include multinanometer-long monodisperse oligomers as models for infinite acetylenic polymers, molecular switches, perethynylated dehydroannulenes, expanded radialenes, and radiaannulenes, and an octamethoxy-substituted expanded cubane with a central C 56 core. Donor-substituted cyanoethynylethenes (CEEs) and 1,1,4,4-tetracyanobuta-1,3-dienes (TCBDs) were introduced as new push-pull chromophores featuring intense intramolecular charge-transfer (CT) interactions. Dendritic multivalent CT chromophores were constructed using atom-economic, "click"-like reactions, and these systems were shown to behave as "molecular batteries", featuring exceptional electron uptake and storage capacity. The research finally led to the development of an unprecedented cascade reaction for the preparation of dendritic and oligomeric donor-acceptor (D-A) molecules. New [AB]-type oligomers become accessible in domino reactions involving repetitive sequences of [2+2] cycloadditions of tetracyanoethylene (TCNE) and tetrathiafulvalene (TTF) to polyynes, followed by retro-electrocyclizations.

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Novel Extended Tetrathiafulvalenes Based on Acetylenic Spacers: Synthesis and Electronic Properties

Cited by 67 publications

References 21 publications

Incorporating Phosphaalkenes into Oligoacetylenes

Incorporating Phosphaalkenes into Oligoacetylenes

New routes to functionalized dihydroazulene photoswitches

Conjugation and optoelectronic properties of acetylenic scaffolds and charge-transfer chromophores

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