Push−Pull Bithienyl Chromophore with an Unusual Transverse Path of Conjugation

Ortiz, Rocío Ponce; Osuna, Reyes Malavé; Hernández, Vı́ctor; Navarrete, Juan T. López; Vercelli, Barbara; Zotti, Gianni; Sumerin, Viktor V.; Баленкова, Е. С.; Nenajdenko, Valentine G.

doi:10.1021/jp0666176

Cited by 5 publications

(1 citation statement)

References 99 publications

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“…Therefore, the study of structure−property relationships to develop new applications is of great importance. − , A very interesting way to achieve structure−property studies is by incorporating nonconventional methods of electronic communication in electron-delocalized molecules. In that respect, the search for alternative modes of interaction between organic π systems has recently led to a variety of new structures with promising electronic features: aromatic derivatives with toroidal delocalization, − spiro compounds, − cross-conjugated molecules, − and π-stacked systems. − In particular, π-stacked systems are very interesting as model compounds in the study of electron-transfer processes mediated by DNA oligonucleotides. ,, …”

Section: Introductionmentioning

confidence: 99%

Efficient Electron Delocalization Mediated by Aromatic Homoconjugation in 7,7-Diphenylnorbornane Derivatives

Barcina¹,

Heras²,

Míriam

et al. 2009

J. Org. Chem.

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Efficient electron delocalization by aromatic homoconjugated 7,7-diphenylnorbornane (DPN) in alternated homoconjugated-conjugated block copolymers and reference compounds is revealed by photophysical and electrochemical measurements. The synthesis of the polymers was achieved by Suzuki polycondensation reaction. Effective electron delocalization by DPN is demonstrated by the significant red shifts observed in the absorption and emission spectra and the variation of the energy band gap of the polymers and monomeric model compounds in comparison to a series of oligophenylenes used as references (p-quaterphenyl, p-terphenyl, and biphenyl). The electron delocalization is also clearly demonstrated by the lower oxidation potential measured for homoconjugated model compound in comparison to p-terphenyl. The results show that the electron delocalization caused by two homoconjugated aryl rings is comparable to the effect produced by one conjugated aryl ring.

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Section: Introductionmentioning

confidence: 99%

Efficient Electron Delocalization Mediated by Aromatic Homoconjugation in 7,7-Diphenylnorbornane Derivatives

Barcina¹,

Heras²,

Míriam

et al. 2009

J. Org. Chem.

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Electron Delocalization in Homoconjugated 7,7‐Diarylnorbornane Systems: A Computational and Experimental Study

Herrero-García

Fernández

Barcina

2011

Chemistry A European J

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A joint computational-experimental study has been carried out to analyze the homoconjugative interactions in 7,7-diarylnorbornane (DPN) derivatives. The experimentally observed new bands in their UV/Vis have been accurately assigned by means of TD-DFT calculations. Both experimental data and computations show that aromatic homoconjugation in acyclic systems is an effective mechanism for electron delocalization that resembles the situation described for polyphenylenes and polyenes. The effective homoconjugation length in homoconjugated oligomers is in the range of 6-7 aryl rings. The effect of substituents directly attached to the para carbon atom of the DPN moiety have been also studied. We found that the HOMO→LUMO vertical transitions can indeed be modified by the nature of the aromatic substituents in order to provoke dramatic changes in the electronic properties (i.e., in the absorption spectra) of the studied species.

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A Joint Experimental and Computational Investigation on Homoconjugated Push‐Pull Chromophores Derived from 7,7‐Diphenylnorbornane

et al. 2012

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We report hereon the synthesis, spectroscopic properties and computational studies of novel aromatic homoconjugated compounds derived from 7,7‐diphenylnorbornane (DPN). The UV/Vis spectra of these compounds show bands corresponding to the respective chromophores as well as new homoconjugation bands and charge transfer absorptions in D–DPN–A push‐pull derivatives. Homoconjugation between the aromatic rings strongly depends on the nature of the substitution at the aryl moieties. Therefore, electronic communication by homoconjugation can be easily tuned by controlling the electronic nature and positions of the substituents. The strong homoconjugative interaction is also reflected in the reactivity, NMR spectra and NLO properties of the compounds studied. DFT calculations nicely agree with the experimental data and shed light on the electronic delocalization via homoconjugation.

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Push−Pull Bithienyl Chromophore with an Unusual Transverse Path of Conjugation

Cited by 5 publications

References 99 publications

Efficient Electron Delocalization Mediated by Aromatic Homoconjugation in 7,7-Diphenylnorbornane Derivatives

Efficient Electron Delocalization Mediated by Aromatic Homoconjugation in 7,7-Diphenylnorbornane Derivatives

Electron Delocalization in Homoconjugated 7,7‐Diarylnorbornane Systems: A Computational and Experimental Study

A Joint Experimental and Computational Investigation on Homoconjugated Push‐Pull Chromophores Derived from 7,7‐Diphenylnorbornane

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