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Dilution-Induced Self-Assembly of Porphyrin Aggregates: A Consequence of Coupled Equilibria

Authors

  • Floris Helmich,

    1. Laboratory of Macromolecular and Organic Chemistry, Institute for Complex Molecular Systems, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven (The Netherlands), Fax: (+31) 40-245-1036
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  • Cameron C. Lee Dr.,

    1. Laboratory of Macromolecular and Organic Chemistry, Institute for Complex Molecular Systems, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven (The Netherlands), Fax: (+31) 40-245-1036
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  • Marko M. L. Nieuwenhuizen,

    1. Laboratory of Macromolecular and Organic Chemistry, Institute for Complex Molecular Systems, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven (The Netherlands), Fax: (+31) 40-245-1036
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  • Jeroen C. Gielen,

    1. Institute for Molecules and Materials, Radboud University Nijmegen, Toernooiveld 7, 6525 ED Nijmegen (The Netherlands)
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  • Peter C. M. Christianen Dr.,

    1. Institute for Molecules and Materials, Radboud University Nijmegen, Toernooiveld 7, 6525 ED Nijmegen (The Netherlands)
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  • Antje Larsen,

    1. Department of Material Science, F.O.R.T.H./I.E.S.L. P.O. Box 1527, 71110 Heraklion (Greece)
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  • George Fytas Prof.,

    1. Department of Material Science, F.O.R.T.H./I.E.S.L. P.O. Box 1527, 71110 Heraklion (Greece)
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  • Philippe E. L. G. Leclère Dr.,

    1. Laboratory for Chemistry of Novel Materials, Université de Mons, 7000 Mons (Belgium)
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  • Albertus P. H. J. Schenning Dr.,

    1. Laboratory of Macromolecular and Organic Chemistry, Institute for Complex Molecular Systems, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven (The Netherlands), Fax: (+31) 40-245-1036
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  • E. W. Meijer Prof. Dr.

    1. Laboratory of Macromolecular and Organic Chemistry, Institute for Complex Molecular Systems, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven (The Netherlands), Fax: (+31) 40-245-1036
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  • This work was supported by the Council of Chemical Sciences of the Netherlands Organization for Scientific Research (CW-NWO). P.E.L.G.L. is Research Associate from FRS-FNRS (Belgium). We would like to thank Maarten Smulders and Tom de Greef for stimulating discussions, Tania Larsen for early contributions to the project, and Prof. Alison Rodger and Dr. Matthew Hicks for assisting with flow linear dichroism experiments.

Abstract

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Piggy-back porphyrins: The presence of a Lewis base remarkably affects the cooperative self-assembly of zinc porphyrins. Driven by the susceptibility of the monomer towards the axial ligand, monomer scavenging caused depolymerization of porphyrin aggregates, and dilution caused aggregation by a re-entrant phase transition. Model predictions were validated by dilution experiments.

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