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Supramolecular zinc phthalocyanine-imidazolyl perylenediimide dyad and triad: Synthesis, complexation, and photophysical studies
- Supramolecular zinc phthalocyanine-imidazolyl perylenediimide dyad and triad: Synthesis, complexation, and photophysical studies
- Cespedes-Guirao F.J.; Ohkubo K.; Fukuzumi S.; Fernandez-Lazaro F.; Sastre-Santos A.
- Ewha Authors
- Shunichi Fukuzumi
- SCOPUS Author ID
- Shunichi Fukuzumi
- Issue Date
- Journal Title
- Chemistry - An Asian Journal
- vol. 6, no. 11, pp. 3110 - 3121
- SCI; SCIE; SCOPUS
- Two new supramolecular architectures based on zinc phthalocyanine (Pc) and imidazolyl-substituted perylenediimide (PDI), ZnPc/DImPDI/ZnPc 1 and ZnPc/ImPDI 2, have been prepared. A strong electron-donor, ZnPc-8, which contained eight tert-octylphenoxy groups was synthesized to ensure high solubility, thereby reducing aggregation in solution and providing δ-donor features while avoiding regioisomeric mixtures. Also, PDI units were functionalized with tert-octylphenoxy groups at the bay positions, which provide solubility to avoid aggregation in solution, together with one and two imidazole moieties in the amide position, PDI-6 and PDI-4, respectively, to be able to strongly coordinate with the ZnPc complex. Supramolecular complexation studies by 1H NMR spectroscopy and ESI-MS demonstrate a high coordinative binding constant between imidazole-substituted PDI-4 or PDI-6 and ZnPc-8. The same results were confirmed by UV/Vis and fluorescence titration studies. UV/Vis titration studies revealed the formation of a 1:1 complex ZnPc/ImPDI 2 for the systems ZnPc-8 and PDI-6 and a 2:1 complex ZnPc/DImPDI/ZnPc 1 for the interaction of ZnPc-8 and PDI-4. The binding constant in both cases was determined to be on the order of 10 5 M -1. Femtosecond laser flash photolysis measurements provided a direct proof of the charge-separated state within both supramolecular assemblies by observing the transient absorption band at 820 nm due to the zinc phthalocyanine radical cation. The lifetimes of charge-separated states are (9.8±3) ns for triad 1 and (3±1) ns for dyad 2. As far as we know, this is the first time that a radical ion pair has been detected in a supramolecular assembled ZnPc-PDI system and has obtained the longest lifetime of a charge-separated state published for ZnPc-PDI assemblies. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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