Closely Stacked Oligo(phenylene ethynylene)s: Effect of π-Stacking on the Electronic Properties of Conjugated Chromophores.

In this work, a bicyclo[4.4.1]undecane scaffold is used to hold oligo(phenylene ethynylene) units in a cofacially stacked arrangement along the entire length of the conjugated units. We study the impact that the resulting strong interchain interactions have on the photophysical properties. The lengt...

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Publicado en:Journal of the American Chemical Society Vol. 134; no. 16; pp. 7176 - 7186
Autores principales: Jagtap, Subodh P., Mukhopadhyay, Sukrit, Coropceanu, Veaceslav, Brizius, Glen L., Brédas, Jean-Luc, Collard, David M.
Formato: Artículo
Publicado: American Chemical Society 4/25/2012
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Acceso en línea:Ver este registro en EBSCOhost
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        atl: Closely Stacked Oligo(phenylene ethynylene)s: Effect of π-Stacking on the Electronic Properties of Conjugated Chromophores.
      aug:
        au:
          Jagtap, Subodh P.
          Mukhopadhyay, Sukrit
          Coropceanu, Veaceslav
          Brizius, Glen L.
          Brédas, Jean-Luc
          Collard, David M.
        affil: School of Chemistry and Biochemistry and Center for Organic Photonics and Electronics, Georgia Institute of Technology Atlanta, Georgia 30332-0400, United States
      su:
        Stacking interactions
        Bioconjugates
        Oligomers
        Density functionals
        Chromophores
        Electric properties
      sug:
        subj:
          Stacking interactions
          Bioconjugates
          Oligomers
          Density functionals
          Chromophores
          Electric properties
      ab: In this work, a bicyclo[4.4.1]undecane scaffold is used to hold oligo(phenylene ethynylene) units in a cofacially stacked arrangement along the entire length of the conjugated units. We study the impact that the resulting strong interchain interactions have on the photophysical properties. The length of the individual oligomer branches was varied from three to five rings to investigate the effect of conjugation on the electronic properties of the stacked segments. Absorption and fluorescence spectra were recorded and compared to those of the corresponding unstacked analogues. Time-dependent density functional theory calculations were carried out and helped to rationalize the low-energy features present in the fluorescence spectra of the stacked systems. The calculations indicate that the low-energy emissions are due to the presence of excimer-like states. The stronger intensity of the low-energy fluorescence band observed in the five-ring stacked system compared to the three-ring analogue is attributed to the smaller activation barrier that separates the local intrachain state and the excimer-like state in the former compound.
      pubtype: Academic Journal
      doctype: Article
      src: R
    language: English
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