Synthesis and Characterization of Extended Tetrathiafulvalenes with Di‐, Tri‐, and Tetraethynylethene Cores

Andersson, Asbjørn Sune; Qvortrup, Katrine; Torbensen, Esben R.; Mayer, Jan-Philipp; Gisselbrecht, Jean‐Paul; Boudon, Corinne; Gross, Maurice; Kadziola, Anders; Kilså, Kristine; Nielsen, Mogens Brøndsted

doi:10.1002/ejoc.200500287

Cited by 39 publications

(20 citation statements)

References 50 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Molecules of choice for opto‐electronic applications are typically constituted of electron‐donating and electron‐accepting groups connected by π‐conjugated bridges . Molecular engineering relies on the proper choice of the building blocks, namely the nature and number of the donor and acceptor moieties, and the nature and length of the conjugated spacers, allowing a fine tuning of the properties of the chromophore,, also modulating the extent of electron transfer between the connected units . On the other hand, the appropriate introduction of substituents on the periphery of the conjugated backbone may promote favourable intermolecular interactions, leading to the preferential formation of ordered assemblies where collective and cooperative effects can enhance the optoelectronic responses, thus widening the range of potential applications of these materials in actual devices .…”

Section: Introductionmentioning

confidence: 99%

Multistimuli‐Responsive Materials from Benzothiadiazole‐Based Charge‐Transfer Chromophores: Interdependence of Optical Properties and Aggregation

et al. 2018

View full text Add to dashboard Cite

A family of multipolar V-shaped chromophores bearing an A'-D-A-D-A' structure were investigated, where 2,1,3-benzothiadiazole, acting as the central electron acceptor (A), is linked to two thiophene-based electron-donating moieties (D) end-capped with alkyl-cyanoacetate substituents (A'). The spectroscopic properties of thin films and powders were investigated and were compared to solutions and nanoaggregates. The optical properties strongly depended on the aggregation state and could be tuned by means of thermal treatment (annealing) of the films and through mechanical treatment (grinding) of the powders, demonstrating that these materials are multistimuli responsive. The spectroscopic analysis revealed the partial formation of J-aggregates both in the films and in powders, despite the weak luminescence. This behavior was interpreted as due to the partial formation of poorly fluorescent red-shifted aggregates acting as a sink in an efficient excitation energytransfer process from J-aggregates.

show abstract

Section: Introductionmentioning

confidence: 99%

Multistimuli‐Responsive Materials from Benzothiadiazole‐Based Charge‐Transfer Chromophores: Interdependence of Optical Properties and Aggregation

et al. 2018

View full text Add to dashboard Cite

show abstract

“…Acetylenic scaffolding with tetraethynylethene (TEE) has provided a large selection of π-conjugated oligomers and macrocycles with interesting optical and redox properties, such as perethynylated poly(triacetylene) oligomers, expanded radialenes, dehydroannulenes, and radiaannulenes. 21 TEE-extended tetrathiafulvalenes (TTFs) 22 and TEEs functionalized with TTF units 23 have also been made; these compounds are very strong chromophores exhibiting intramolecular charge-transfer absorptions as the TEE core behaves as an electron acceptor and TTF (or dithiafulvene unit) behaves as an electron donor.…”

Section: Short Review Syn Thesis 5 Acetylenic Scaffolding With Tetraementioning

confidence: 99%

Sonogashira-Like Coupling Reactions with Phosphine–Gold(I) Alkynyl Complexes

Nielsen

2016

Synthesis

View full text Add to dashboard Cite

Phosphine-gold(I) alkynyl complexes are stable compounds that can be subjected to palladium-catalyzed cross-coupling reactions. This article outlines the synthesis of such compounds and their ability to play the role as substrates in Sonogashira couplings is covered. This synthetic approach is particularly attractive when the related terminal alkynes are unstable. 1 Introduction 2 Phosphine-Gold(I) Alkynyl Complexes 3 Sonogashira-Like Couplings 4 Transmetalation Step-Mechanistic Insight 5 Acetylenic Scaffolding with Tetraethynylethene Derivatives 6 Conclusion

show abstract

“…The yield of 22 was rather low, but we have often, for unknown reasons, experienced low yields when employing the terminal alkyne of 6 in cross-coupling reactions [37,38].…”

Section: Functionalization Of the Five-membered Ring With Dtf And Ttfmentioning

confidence: 99%

New routes to functionalized dihydroazulene photoswitches

Nielsen

Broman

Petersen

et al. 2010

Pure and Applied Chemistry

Self Cite

View full text Add to dashboard Cite

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.

show abstract

Synthesis and Characterization of Extended Tetrathiafulvalenes with Di‐, Tri‐, and Tetraethynylethene Cores

Cited by 39 publications

References 50 publications

Multistimuli‐Responsive Materials from Benzothiadiazole‐Based Charge‐Transfer Chromophores: Interdependence of Optical Properties and Aggregation

Multistimuli‐Responsive Materials from Benzothiadiazole‐Based Charge‐Transfer Chromophores: Interdependence of Optical Properties and Aggregation

Sonogashira-Like Coupling Reactions with Phosphine–Gold(I) Alkynyl Complexes

New routes to functionalized dihydroazulene photoswitches

Contact Info

Product

Resources

About