Oligophenylenevinylenes in Spatially Confined Nanochannels: Monitoring Intermolecular Interactions by UV/Vis and Raman Spectroscopy

Authors

  • Mariya Aloshyna,

    1. Istituto per lo Studio delle Macromolecole, CNR Via Bassini 15, 20133 Milano (Italy)
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  • Begoña Milián Medina,

    1. Laboratory for Chemistry of Novel Materials, Center for Research in Molecular Electronics and Photonics, University of Mons-Hainaut Place du Parc 20, 7000 Mons (Belgium)
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  • Lars Poulsen,

    1. Institute for Physical and Theoretical Chemistry, University of Tübingen Auf der Morgenstelle 8, 72076 Tübingen (Germany)
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  • Juliette Moreau,

    1. Dipartimento di Chimica Organica e Industriale, Università di Milano Via Venezia 21, 20133 Milano (Italy)
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  • David Beljonne,

    1. Laboratory for Chemistry of Novel Materials, Center for Research in Molecular Electronics and Photonics, University of Mons-Hainaut Place du Parc 20, 7000 Mons (Belgium)
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  • Jérôme Cornil,

    1. Laboratory for Chemistry of Novel Materials, Center for Research in Molecular Electronics and Photonics, University of Mons-Hainaut Place du Parc 20, 7000 Mons (Belgium)
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  • Giuseppe Di Silvestro,

    1. Dipartimento di Chimica Organica e Industriale, Università di Milano Via Venezia 21, 20133 Milano (Italy)
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  • Michele Cerminara,

    1. Dipartimento di Scienza dei Materiali, Università degli Studi di Milano Bicocca Via Cozzi 53, 20125 Milano (Italy)
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  • Francesco Meinardi,

    1. Dipartimento di Scienza dei Materiali, Università degli Studi di Milano Bicocca Via Cozzi 53, 20125 Milano (Italy)
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  • Riccardo Tubino,

    1. Dipartimento di Scienza dei Materiali, Università degli Studi di Milano Bicocca Via Cozzi 53, 20125 Milano (Italy)
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  • Heiner Detert,

    1. Institute for Organic Chemistry, University of Mainz Duesbergweg 10-14, 55099 Mainz (Germany)
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  • Sigurd Schrader,

    1. Engineering Physics, Technische Fachhochschule Wildau Friedrich-Engels-Str. 63, D-15745 Wildau (Germany)
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  • Hans-Joachim Egelhaaf,

    1. Institute for Physical and Theoretical Chemistry, University of Tübingen Auf der Morgenstelle 8, 72076 Tübingen (Germany)
    2. Egelhaaf Christian-Doppler Laboratory for Surface Optical Methods, Johannes-Kepler University Altenberger Str. 69, 4040 Linz (Austria)
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  • Chiara Botta,

    1. Istituto per lo Studio delle Macromolecole, CNR Via Bassini 15, 20133 Milano (Italy)
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  • Johannes Gierschner

    Corresponding author
    1. Laboratory for Chemistry of Novel Materials, Center for Research in Molecular Electronics and Photonics, University of Mons-Hainaut Place du Parc 20, 7000 Mons (Belgium)
    2. Institute for Physical and Theoretical Chemistry, University of Tübingen Auf der Morgenstelle 8, 72076 Tübingen (Germany)
    • Laboratory for Chemistry of Novel Materials, Center for Research in Molecular Electronics and Photonics, University of Mons-Hainaut Place du Parc 20, 7000 Mons (Belgium).
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  • The authors would like to acknowledge the financial support by the European Commission through the Human Potential Program within the 5th and 6th framework programme (RTN ‘Nanochannel’, Contract No. HPRN-CT-2002-00323, and RTN ‘Nanomatch’, MRTN-CT-2006-035884). The group in Mons is grateful to Prof. J. R. Reimers (University of Sidney, Australia) for making available a version of his recently developed DUSHIN program, and K. Schmidt (Georgia Institute of Technology, Atlanta, USA) for adapting TURBOMOLE output files to the DUSHIN input. B. M. M. acknowledges the Ministerio de Educación y Ciencia of Spain for a postdoctoral grant. J. C. and D. B. are research associates of the Belgian National Fund for Scientific Research (FNRS). The groups in Milan wish to thank FIRB-MURST “Synergy” and CARIPLO foundation for financial support.

Abstract

Perhydrotriphenylene-based channel-forming inclusion compounds (ICs) and thin films made of polyphenylenevinylene (PPV)-type oligomers with terminal alkoxy groups are investigated and compared in a combined experimental and theoretical approach. Interchromophore interactions and host-guest interactions are elucidated by UV/Vis and Raman spectroscopy. The impact of the local environment of the chromophore on the optical and photophysical properties is discussed in light of quantum-chemical calculations. In stark contrast to thin films where preferential side-by-side orientation leads to quenching of photoluminescence (PL) via non-emissive traps, the ICs are found to be attractive materials for opto-electronic applications: they offer high chromophore concentrations, but at the same time behave as quasi-isolated entities of tightly packed, well-oriented objects with high PL quantum yields and the possibility of color tuning.

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