Perylene diimide-appended mixed (phthalocyaninato)(porphyrinato) europium(III) double-decker complex: Synthesis, spectroscopy and electrochemical properties

Treatment of sandwich-type mixed (phthalocyaninato)(porphyrinato) metal complex [HEuIII{Pc(α-3-OC5H11)4}{TriBPP(NH2)}] (3) [Pc(α-3-OC5H11)4 = 1,8,15,22-tetrakis(3-pentyloxy)-phthalocyaninate, TriBPP(NH2) = 5,10,15-tris(4-tert-butylphenyl)-20-(4-aminophenyl)porphyrinate] with N-n-butyl-1,6,7,12-tetra(4-tert-butylphenoxyl)perylene-3,4-dicarboxylate anhydride-9,10-dicarboxylate imide (2) in the presence of imidazole in toluene afforded the novel perylene diimide-appended mixed (phthalocyaninato)(porphyrinato) europium(III) double-decker complex (5). Porphyrin–PDI dyad 4 was also obtained by similar method. The electronic absorption spectroscopic and electrochemical properties of PDI-appended double-decker 5 and the model compounds 2, 3, and 4 were studied, the results indicated that there was no considerable ground-state interaction between the double-decker unit and the PDI unit in 5. The fluorescence measurements revealed that the emission of PDI unit was effectively quenched by the double-decker unit, suggesting remarkable intramolecular interaction in 5 under excited state.

A novel phthalocyanine–porphyrin–PDI array containing a sandwich-type mixed (phthalocyaninato)(porphyrinato) europium(III) double-decker core and a PDI modifier was designed and synthesized. The steady-state electronic absorption and electrochemical studies indicated that there was no ground-state interaction between the double-decker unit and the PDI unit. The fluorescence measurements revealed that the emission of PDI unit was remarkably quenched by the double-decker unit, suggesting considerable intramolecular interaction under excited state.Figure optionsDownload as PowerPoint slideHighlights
► A PDI-appended mixed Eu(Pc)(Por) double-decker complex was synthesized.
► The electronic absorption and electrochemical properties were studied. Interaction between the double-decker unit and the PDI unit was not observed at ground state.
► The emission of PDI unit was quenched by the double-decker unit. Considerable intramolecular interaction exists at excited state.