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Probing Supramolecular Interactions between a Crown Ether Appended Zinc Phthalocyanine and an Ammonium Group Appended to a C 60 Derivative
Author(s) -
Lederer Marcus,
Hahn Uwe,
Strub JeanMarc,
Cianférani Sarah,
Van Dorsselaer Alain,
Nierengarten JeanFrançois,
Torres Tomas,
Guldi Dirk M.
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201503315
Subject(s) - chemistry , phthalocyanine , supramolecular chemistry , photochemistry , crown ether , electrospray ionization , zinc , intermolecular force , dication , fullerene , crystallography , organic chemistry , molecule , ion , crystal structure
Self‐assembly driven by crown ether complexation of zinc phthalocyanines equipped with one 18‐crown‐6 moiety and fullerenes bearing an ammonium head group afforded a novel donor–acceptor hybrid. In reference experiments, fullerenes containing a Boc‐protected amine functionality have been probed. The circumvention of zinc phthalocyanine aggregation is important for the self‐assembly, which required the addition of pyridine. From absorption and fluorescence titration assays, which provided sound and unambiguous evidence for mutual interactions between the electron donor and the electron acceptor within the hybrids, association constants in the order of 8.0×10 5 m −1 have been derived. The aforementioned is based on 1:1 stoichiometries, which have been independently confirmed by Job's plot measurements. In the excited state, which has been examined by transient absorption experiments, intermolecular charge separation evolves from the photoexcited zinc phthalocyanine to the fullerene subunit and leads to short‐lived charge‐separated states. Interestingly, photoexcitation of zinc phthalocyanine dimers/aggregates can also be followed by an intermolecular charge separation between vicinal phthalocyanines. These multicomponent supramolecular ensembles have also been shown by in‐depth electrospray ionization mass spectrometry (ESI‐MS) studies, giving rise to the formation and detection of a variety of non‐covalently linked species.