Krokos E, Spänig F, Ruppert M, Hirsch A, Guldi DM (2012)
Publication Type: Journal article, Original article
Publication year: 2012
Original Authors: Krokos E., Spänig F., Ruppert M., Hirsch A., Guldi D.M.
Publisher: Wiley-VCH Verlag
Book Volume: 18
Pages Range: 10427-10435
Journal Issue: 33
Photophysical investigations on a series of (2,4,6)-tris-substituted metalloporphyrin-fullerene conjugates revealed the effects of an electron-rich microenvironment surrounding the electron-donating porphyrin as a function of the metal center. On one hand, for all conjugates-water-soluble and non-water-soluble-ultrafast charge separation was observed upon photoexcitation. On the other hand, when examining the charge recombination dynamics for the non-water-soluble conjugates it becomes obvious that the (2,4,6)-tris- substitution stabilizes the radical-ion-pair state relative to the mono-substitution in the ortho-, meta-, and para-position. The more efficient protection of the electron-donating porphyrin from solvation is thought to be the major cause for this impact. Nevertheless, the situation is slightly different for the water-soluble conjugates. At first glance, the radical-ion-pair state lifetimes are, also in the case of the (2,4,6)-tris-substitution, longer than for the mono-substituted ortho-, meta- and para-conjugates. Upon closer inspection, they fail, however, to exhibit any metal dependence. Competing with the protection from solvation of the dendrons, dipole-charge interactions impact the stabilization in the polar aqueous environment and, in turn, become the dominant force governing the electron-transfer dynamics. Caged porphyrins: Photophysical and photochemical characterization of a series of porphyrin-fullerene conjugates have been performed. The conjugates are intended to act as mimics of the photosynthetic center and emphasis was placed on the dependence of microenvironmental effects on electron-transfer dynamics (see figure). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
APA:
Krokos, E., Spänig, F., Ruppert, M., Hirsch, A., & Guldi, D.M. (2012). Dendritic metalloporphyrin-fullerene conjugates: Changing the microenvironment around redox-active centers and its impact on charge-transfer reactions. Chemistry - A European Journal, 18(33), 10427-10435. https://dx.doi.org/10.1002/chem.201202110
MLA:
Krokos, Evangelos, et al. "Dendritic metalloporphyrin-fullerene conjugates: Changing the microenvironment around redox-active centers and its impact on charge-transfer reactions." Chemistry - A European Journal 18.33 (2012): 10427-10435.
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