Cooperativity and tunable excited state deactivation: Modular self-assembly of depsipeptide dendrons on a Hamilton receptor modified porphyrin platform

Gnichwitz JF, Wielopolski M, Hartnagel K, Hartnagel U, Guldi DM, Hirsch A (2008)


Publication Type: Journal article, Original article

Publication year: 2008

Journal

Original Authors: Gnichwitz J.-F., Wielopolski M., Hartnagel K., Hartnagel U., Guldi D.M., Hirsch A.

Publisher: American Chemical Society

Book Volume: 130

Pages Range: 8491-8501

Journal Issue: 26

DOI: 10.1021/ja8018065

Abstract

A series of novel supramolecular architectures were built around a tin tetraphenyl porphyrin platform 6 - functionalized by a 2-fold 1-ethyl-3-3-(3-dimethylaminopropyl)carbodiimide (EDC) promoted condensation reaction - and chiral depsipeptide dendrons of different generations 1-4. Here, implementation of a Hamilton receptor provided the necessary means to keep the constituents together via strong hydrogen bonding. Characterization of all architectures has been performed, including 4 which is the fourth generation, on the basis of NMR and photophysical methods. In particular, several titration experiments were conducted suggesting positive cooperativity, an assessment that is based on association constants that tend to be higher for the second binding step than for the first step. Importantly, molecular modeling calculations reveal a significant deaggregation of the intermolecular network of 6 during the course of the first binding step. As a consequence, an improved accessibility of the second Hamilton receptor unit in 6 emerges and, in turn, facilitates the higher association constants. The features of the equilibrium, that is, the dynamic exchange of depsipeptide dendrons 1-4 with fullerene 5, was tested in photophysical reference experiments. These steady-state and time-resolved measurements showed the tunable excited-state deactivations of these complexes upon photoexcitation. © 2008 American Chemical Society.

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APA:

Gnichwitz, J.-F., Wielopolski, M., Hartnagel, K., Hartnagel, U., Guldi, D.M., & Hirsch, A. (2008). Cooperativity and tunable excited state deactivation: Modular self-assembly of depsipeptide dendrons on a Hamilton receptor modified porphyrin platform. Journal of the American Chemical Society, 130(26), 8491-8501. https://doi.org/10.1021/ja8018065

MLA:

Gnichwitz, Jan-Frederik, et al. "Cooperativity and tunable excited state deactivation: Modular self-assembly of depsipeptide dendrons on a Hamilton receptor modified porphyrin platform." Journal of the American Chemical Society 130.26 (2008): 8491-8501.

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