title: A supramolecular photosynthetic model made of a multiporphyrinic array constructed around a C60 core and a C60-imidazole derivative.
abstract: The photophysical properties of a supramolecular fullerene-porphyrin ensemble resulting from the self-assembly of a pyrrolidinofullerene-imidazole derivative (F1) with a multimetalloporphyrin array constructed around a hexasubstituted fullerene core (F(ZnP)12) have been investigated. The fullerene hexa-adduct core of the host system does not play any active role in the cascade of photoinduced events of the supramolecular ensemble, indeed no intercomponent photoinduced processes could be observed in host F(ZnP)12. In contrast, upon axial coordination with the monosubstituted fullerene guest F1, a quantitative quenching of the fluorescence signal of the metalloporphyrins was observed for the supramolecular complex [F(ZnP)12(F1)n] both in polar and nonpolar solvents. In toluene, the supramolecular ensemble exhibits a charge transfer emission centered around nm, suggesting the occurrence of intramolecular face-to-face interactions of F1 with neighboring metalloporphyrin moieties within the self-assembled photoactive array. This mechanism is supported by the fact that a one order of magnitude increase in the binding constant was observed for the supramolecular complex [F(ZnP)12(F1)n] when compared with a reference system lacking the pyrrolidinofullerene unit. In benzonitrile, a long-lived charge-separated state (τ=0.3 μs) has been detected for the supramolecular adduct.
authors: Istituto per la Sintesi Organica e la Fotoreattività, Consiglio Nazionale delle Ricerche, Via Gobetti 101, 40129 Bologna (Italy); Present address: Photosciences and Photonics, Chemical Sciences and Technology Division, CSIR-National Institute for Interdisciplinary Science and Technology, Thiruvananthapuram 695 019, Kerala (India).
authors: K
authors: K
authors: Yoosaf
authors: Julien
authors: J
authors: Iehl
authors: Iwona
authors: I
authors: Nierengarten
authors: Mohamed
authors: M
authors: Hmadeh
authors: Anne-Marie
authors: AM
authors: Albrecht-Gary
authors: Jean-François
authors: JF
authors: Nierengarten
authors: Nicola
authors: N
authors: Armaroli
mesh_terms: D056831:Coordination Complexes / Q000737:chemistry; D004579:Electron Transport; D004735:Energy Transfer; D037741:Fullerenes / Q000737:chemistry*; D007093:Imidazoles / Q000737:chemistry*; D008665:Metalloporphyrins / Q000737:chemistry; D009570:Nitriles / Q000737:chemistry; D010788:Photosynthesis; D012997:Solvents / Q000737:chemistry; D015032:Zinc / Q000737:chemistry
chemical_list: D056831:Coordination Complexes; D037741:Fullerenes; D007093:Imidazoles; D008665:Metalloporphyrins; D009570:Nitriles; D012997:Solvents; C029899:imidazole; C014356:benzonitrile; D015032:Zinc; C069837:fullerene C60
keywords: electron transfer; energy transfer; fullerenes; porphyrins; self-assembly