Lederer Marcus, Hahn Uwe, Strub Jean-Marc, Cianférani Sarah, Van Dorsselaer Alain, Nierengarten Jean-François, Torres Tomas, Guldi Dirk M
Department of Chemistry and Pharmacy, Interdisciplinary Center for Molecular Materials (ICMM), Friedrich-Alexander-Universität Erlangen-, Nürnberg, Egerlandstrasse 3, 91058, Erlangen, Germany), Fax.
Departamento de Química Orgánica, Universidad Autónoma de Madrid, 28049, Madrid, Spain), Fax.
Chemistry. 2016 Feb;22(6):2051-2059. doi: 10.1002/chem.201503315. Epub 2016 Jan 7.
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 m 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.
由带有一个18-冠-6部分的锌酞菁与带有铵头基的富勒烯通过冠醚络合驱动的自组装产生了一种新型供体-受体杂化物。在参考实验中，对含有Boc保护胺官能团的富勒烯进行了研究。避免锌酞菁聚集对于自组装很重要，这需要添加吡啶。通过吸收和荧光滴定分析，为杂化物中电子供体和电子受体之间的相互作用提供了可靠且明确的证据，得出的缔合常数约为8.0×10 m。上述结果基于1:1的化学计量比，这已通过乔布氏图测量得到独立证实。在通过瞬态吸收实验研究的激发态下，分子间电荷分离从光激发的锌酞菁向富勒烯亚基演化，并导致短寿命的电荷分离态。有趣的是，锌酞菁二聚体/聚集体的光激发也可以伴随着相邻酞菁之间的分子间电荷分离。深入的电喷雾电离质谱（ESI-MS）研究也表明了这些多组分超分子聚集体的存在，从而形成并检测到了多种非共价连接的物种。
