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Modulating Charge‐Transfer Interactions in Topologically Different Porphyrin–C 60 Dyads
Author(s) -
Guldi Dirk M.,
Hirsch Andreas,
Scheloske Michael,
Dietel Elke,
Troisi Alessandro,
Zerbetto Francesco,
Prato Maurizio
Publication year - 2003
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.200304995
Subject(s) - intramolecular force , porphyrin , electron transfer , chemical physics , charge (physics) , chemistry , molecular physics , spectral line , molecular dynamics , electron , absorption (acoustics) , polarity (international relations) , absorption spectroscopy , marcus theory , range (aeronautics) , photochemistry , atomic physics , materials science , computational chemistry , reaction rate constant , physics , kinetics , optics , stereochemistry , quantum mechanics , astronomy , composite material , biochemistry , cell
Control over the interchromophore separation, their angular relationship, and the spatial overlap of their electronic clouds in several ZnP – C 60 dyads ( ZnP =zinc porphyrin) is used to modulate the rates of intramolecular electron transfer. For the first time, a detailed analysis of the charge transfer absorption and emission spectra, time‐dependent spectroscopic measurements, and molecular dynamics simulations prove quantitatively that the same two moieties can produce widely different electron‐transfer regimes. This investigation also shows that the combination of ZnP and C 60 consistently produces charge recombination in the inverted Marcus region, with reorganization energies that are remarkably low, regardless of the solvent polarity. The time constants of electron transfer range from the μs to the ps regime, the electronic couplings from a few tens to several hundreds of cm −1 , and the reorganization energies remain below 0.54 eV and can be as low as 0.16 eV.