Synthesis and Optical Properties of all‐<i>trans</i>‐Oligodiacetylenes

Pilzak, Gregor S.; Lagen, Barend van; Hendrikx, Cindy C. J.; Sudhölter, Ernst J. R.; Zuilhof, Han

doi:10.1002/chem.200800241

Cited by 28 publications

(57 citation statements)

References 72 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This bathochromic shift is similar to literature data reported for shorter enyne-based oligomer series reported by others [13,17,18] and us, [12,15] and becomes smaller with chain elongation: Dl max decreases from % 0.34 eV going from 1-1 to 1-2 (in both n- …”

Section: Steady-state Absorption In Solutionsupporting

confidence: 91%

“…[15] The protodesilylation of oligodiacetylene 2-n using a mild alkaline method proceeded quantitatively and resulted in the formation of terminal acetylenes 3-n, as shown in Figure 2.…”

Section: Resultsmentioning

confidence: 98%

“…To increase the rate of the reaction and to minimize formation of side products, the concentration of the tetrakis(triphenylphosphine)palladium catalyst and Cu(I) cocatalyst was kept slightly higher (> 5 mol%) than used previously; in the case when the crosscoupled Sonogashira product was the target. [15] Under such optimized conditions the homocoupling of long oligomers proceeded almost quantitatively (> 90 % isolated yields) and all coupling reactions were completed within 3 h.…”

Section: Resultsmentioning

confidence: 99%

“…[10] Oligomers based on repeating enyne units, such as oligodiacetylenes, act as models of polydiacetylene (PDA) for understanding the influence of the precise conjugation length on the electronic properties. [11][12][13][14][15] Recently, we have published an iterative approach to construct a new series of A C H T U N G T R E N N U N G oligoA C H T U N G T R E N N U N G diacetylenes ranging from monomer up to octamer bearing 17 conjugated double and triple bonds. In this study we extend our method [15] to produce nanometer-sized materials reaching up to 30 conjugated double and triple bonds with an estimated length of % 8 nm.…”

Section: Introductionmentioning

confidence: 99%

“…[11][12][13][14][15] Recently, we have published an iterative approach to construct a new series of A C H T U N G T R E N N U N G oligoA C H T U N G T R E N N U N G diacetylenes ranging from monomer up to octamer bearing 17 conjugated double and triple bonds. In this study we extend our method [15] to produce nanometer-sized materials reaching up to 30 conjugated double and triple bonds with an estimated length of % 8 nm.…”

Section: Introductionmentioning

confidence: 99%

See 4 more Smart Citations

Synthesis and Optoelectronic Properties of Nanometer‐Sized and Highly Soluble Homocoupled Oligodiacetylenes

Pilzak¹,

Baggerman²,

Lagen³

et al. 2009

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

A new series of pure, nanometer-sized and highly-soluble homocoupled oligodiacetylenes (HODA) consisting of two symmetrical oligodiacetylene units was synthesized with high yield and on a multi-milligram scale under mild, catalytic Sonogashira conditions. The lambda(max) and the epsilon(max) of absorption for these HODAs show an increase with the chain elongation. The lambda(max) converges to 450 nm for the longest members of the series at micromolar concentration and to 462 nm for thin drop-casted films. An additional red-shifted absorption is observed in the solid state and in solution at low temperatures, which is caused by aggregation. The lambda(max) of the fluorescence emission increases with the chain length and reaches 492 nm for the longest oligomer. The fluorescence quantum yield has its maximum for the shortest oligomer and decreases rapidly for the longer ones. A similar trend is found for the fluorescence lifetime with a maximum of 100 ps for the homocoupled monomer. The rotational correlation time shows a linear increase with the oligomer length. This reveals a significant persistence length and indicates that the HODA molecules are fully stretched molecular rods (up to 8.2 nm).

show abstract

Section: Steady-state Absorption In Solutionsupporting

confidence: 91%

“…[15] The protodesilylation of oligodiacetylene 2-n using a mild alkaline method proceeded quantitatively and resulted in the formation of terminal acetylenes 3-n, as shown in Figure 2.…”

Section: Resultsmentioning

confidence: 98%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Synthesis and Optoelectronic Properties of Nanometer‐Sized and Highly Soluble Homocoupled Oligodiacetylenes

Pilzak¹,

Baggerman²,

Lagen³

et al. 2009

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

show abstract

Optisch reine, monodisperse cis‐Oligodiacetylene: Chiralitätsverstärkung durch Aggregation

Chernick

Borzsonyi

Steiner³

et al. 2013

Angewandte Chemie

View full text Add to dashboard Cite

Konformationsänderungen des konjugierten Rückgrats von Poly-und Oligodiacetylenen (PDAs und ODAs) spielen bei der Bestimmung der elektronischen Eigenschaften dieser Verbindungen eine wichtige Rolle. Gleichzeitig kçnnen Konformationsänderungen auch zu gefalteten Strukturen führen, die helikale Chiralität aufweisen. Durch Verwendung von d-Campher als chiraler Baustein konnten monodisperse, optisch reine cis-Oligodiacetylene (ODAs) in hoher Ausbeute erhalten werden. cis-ODAs bis zur Länge des Tridecamers wurden synthetisiert, was dem längsten bisher bekannten monodispersen cis-ODA entspricht. UV/Vis-Spektroskopie deutet auf eine hohe effektive Konjugationslänge in THF hin, vermutlich aufgrund einer linearen planaren Konformation in diesem Lçsungsmittel. Hochauflçsende STM/AFM-Messungen von Filmen des Nonamers, abgeschieden aus einer THF-Lçsung auf HOPG, zeigen eine lineare Struktur. In iPrOH gemessene Zirkulardichroismus(CD)-Spektren legen die Bildung chiraler Aggregate der ODAs mit mindestens neun d-Campher-Einheiten nahe. Die CD-Resonanz ist konzentrations-und temperaturabhängig.Polydiacetylene (PDAs) sind ausgiebig untersucht worden, [1] während Oligodiacetylene (ODAs) häufig als hilfreiche Modelle für die Untersuchung oder Vorhersage von Eigenschaften der PDAs herangezogen werden. [2] Es ist beispielsweise bekannt, dass trans-PDAs chromatische Eigenschaften aufweisen, ein Merkmal das zum Aufbau molekularer Schalter und Sensoren genutzt werden kann. [1] Die elektronischen Eigenschaften von PDAs sind häufig von der effektiven Konjugationslänge ("effective conjugation length", ECL) abhängig, [3] wodurch Konformationseinflüsse, z. B. die helikale Faltung des p-konjugierten Rückgrats, ausschlaggebend sind. [4] trans-PDAs/ODAs zeigen üblicherweise eine hçhere ECL als cis-ODAs, bedingt durch die gefaltete Struktur der cis-ODAs in Lçsung. [5] Eine helikale Konformation kann zwar die ECL einschränken, vermittelt jedoch "Händigkeit", also Chiralität. Lässt sich die Drehrichtung des helikalen "Foldamers" kontrollieren, so kann man auf die Chiralität Einfluss nehmen, wodurch Anwendungen als chirale molekulare Sensoren und Schalter [6] oder chirale leitende Polymere [7] zugänglich werden.trans-PDAs/ODAs sind seit der bahnbrechenden Arbeit von Wegner ausführlich studiert worden, [8] wohingegen über cis-PDAs/ODAs sehr viel weniger bekannt ist. [9] Bisher wurden cis-ODAs ausschließlich über iterative Synthesewege hergestellt. [5,10] Für eine effiziente cis-ODA-Synthese muss die cis-trans-Isomerisierung unterbunden werden, was durch die Verwendung eines Ringsystems ermçglicht wird, das eine cis-Geometrie erzwingt. Beispiele für diese Strategie beinhalten die Verwendung von Cyclopentenringen, wie von Hirsch und Mitarbeitern berichtet, [5] oder die Verwendung eines Arylrings, was zu einer strukturell artverwandten Klasse von Oligomeren, den ortho-Arylenethinylenen, führt. [11] Für die Entwicklung monodisperser, optisch reiner ODAs sahen wir einen chiralen Kohlenwasserstoffring vor, dessen Konformation dynamisch durch solvophobe ...

show abstract

Tailored Palladium Catalysts for Selective Synthesis of Conjugated Enynes by Monocarbonylation of 1,3‐Diynes

et al. 2020

View full text Add to dashboard Cite

For the first time, the monoalkoxycarbonylation of easily available 1,3‐diynes to give synthetically useful conjugated enynes has been realized. Key to success was the design and utilization of the new ligand 2,2′‐bis(tert‐butyl(pyridin‐2‐yl)phosphanyl)‐1,1′‐binaphthalene (Neolephos), which permits the palladium‐catalyzed selective carbonylation under mild conditions, providing a general preparation of functionalized 1,3‐enynes in good‐to‐high yields with excellent chemoselectivities. Synthetic applications that showcase the possibilities of this novel methodology include an efficient one‐pot synthesis of 4‐aryl‐4H‐pyrans as well as the rapid construction of various heterocyclic, bicyclic, and polycyclic compounds.

show abstract

Synthesis and Optical Properties of all‐trans‐Oligodiacetylenes

Cited by 28 publications

References 72 publications

Synthesis and Optoelectronic Properties of Nanometer‐Sized and Highly Soluble Homocoupled Oligodiacetylenes

Synthesis and Optoelectronic Properties of Nanometer‐Sized and Highly Soluble Homocoupled Oligodiacetylenes

Optisch reine, monodisperse cis‐Oligodiacetylene: Chiralitätsverstärkung durch Aggregation

Tailored Palladium Catalysts for Selective Synthesis of Conjugated Enynes by Monocarbonylation of 1,3‐Diynes

Contact Info

Product

Resources

About