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Synthesis and Photophysical Properties of Fullerene–Phthalocyanine–Porphyrin Triads and Pentads
Author(s) -
Enes Roger F.,
Cid JuanJosé,
Hausmann Anita,
Trukhina Olga,
Gouloumis Andreas,
Vázquez Purificación,
Cavaleiro José A. S.,
Tomé Augusto C.,
Guldi Dirk M.,
Torres Tomás
Publication year - 2012
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201102819
Subject(s) - phthalocyanine , chemistry , photochemistry , intramolecular force , porphyrin , singlet state , cycloaddition , excited state , fullerene , tetrathiafulvalene , stereochemistry , molecule , catalysis , organic chemistry , physics , nuclear physics
The synthesis and photophysical properties of several fullerene–phthalocyanine–porphyrin triads ( 1 – 3 ) and pentads ( 4 – 6 ) are described. The three photoactive moieties were covalently connected in an one‐step synthesis through 1,3‐dipolar cycloaddition to C 60 of the corresponding azomethine ylides generated in situ by condensation reaction of a substituted N ‐porphyrinylmethylglycine derivative and an appropriated formyl phthalocyanine or a diformyl phthalocyanine derivative, respectively. ZnP‐C 60 ‐ZnPc ( 3 ), (ZnP) 2 ‐ZnPc‐(C 60 ) 2 ( 6 ), and (H 2 P) 2 ‐ZnPc‐(C 60 ) 2 ( 5 ) give rise upon excitation of their ZnP or H 2 P components to a sequence of energy and charge‐transfer reactions with, however, fundamentally different outcomes. With (ZnP) 2 ‐ZnPc‐(C 60 ) 2 ( 6 ) the major pathway is an highly exothermic charge transfer to afford (ZnP)(ZnP .+ )‐ZnPc‐(C 60 .− )(C 60 ). The lower singlet excited state energy of H 2 P (i.e., ca. 0.2 eV) and likewise its more anodic oxidation (i.e., ca. 0.2 V) renders the direct charge transfer in (H 2 P) 2 ‐ZnPc‐(C 60 ) 2 ( 5 ) not competitive. Instead, a transduction of singlet excited state energy prevails to form the ZnPc singlet excited state. This triggers then an intramolecular charge transfer reaction to form exclusively (H 2 P) 2 ‐ZnPc .+ ‐(C 60 .− )(C 60 ). A similar sequence is found for ZnP‐C 60 ‐ZnPc ( 3 ).