10.1002/anie.201802443
Angewandte Chemie International Edition
COMMUNICATION
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Figure 5. Schematic illustration of the charge recombination processes (blue
arrows) observed in (a, b) 1•+⊃(C60 •- and (c) 1•+⊃(C60 •-1.
) )
2 2
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Only one electron recombination process was observed in the
more symmetric 2:1 complex (1(C60)21, Figure 5c). However,
by virtue of charge delocalization in the porphyrin•+-
[10]CPP(C60)2•-[10]CPP-porphyrin charge-separated state,
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•-
and in stark contrast to the 1•+C60 system, a lifetime of up to
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541.8±112.8 ns was observed,29 which is among the longest-lived
charge-separated states in fullerene / porphyrin containing
electron donor-acceptor systems.30 This first study of
intra(supra)molecular electron transfer to (C60)2,31 attests to the
unique potential of our modular, non-covalent approach.
Nevertheless, it should be noted that, despite the conformational
rigidity of our entire system and the high association constants,
our results reflect average values, particularly in respect to
fullerene rotation and translation (“shuttling” of (C60)2)31a within the
CPP host.
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In conclusion, we have successfully carried out the synthesis
of
a porphyrin-[10]CPP conjugate and studied its strong
association with a range of fullerenes. Pump probe spectroscopy
demonstrated that [10]CPP as a supramolecular junction enables
efficient charge transport between a porphyrin electron donor and
unmodified fullerene electron acceptors. These results, together
with Yamago’s recent report on the thin-film conductivity of
[10]CPP and its alkoxy derivatives,32 imply that supramolecular
complexes of [10]CPP and fullerenes may be a useful addition to
the toolbox of organic electronics.33
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Acknowledgements
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We are grateful for financial support from the DFG (SFB953:
“Synthetic Carbon Allotropes”), the University of Ulm and FAU
Erlangen-Nürnberg. Fabian Fritze and Pascal Frick are
acknowledged for preparing a batch of (C60)2.
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[15] Due to the energy transfer from CPP unit to porphyrin, the quantum
yields of CPP unit in porphyrin-[10]CPP is only 0.44% when we use 340
nm excitation. See Figure S3.
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Chem. Eur. J. 2013, 19, 14061–14068.
Keywords: electron transfer • host-guest systems • time-
resolved spectroscopy • strained molecules • fullerenes
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