title: Enhancing molecular recognition in electron donor-acceptor hybrids via cooperativity.
abstract: Herein, we report the synthesis of guanidinium bis-porphyrin tweezers 1 and fullerene carboxylate 3, their assembly into a novel supramolecular 1@3 electron donor-acceptor hybrid, and its characterization. In solution, the binding constant affording 1@3 is exceptionally high. 1@3, which features a highly confined topography, builds up from a combination of guanidinium-carboxylate hydrogen bonding and π-π stacking/charge-transfer motifs. The latter is governed by interactions between the electron-donating porphyrin and the electron-accepting fullerene. Importantly, positive cooperativity between the applied binding motifs is corroborated by a number of experimental techniques, such as NMR, absorption, fluorescence, etc. In addition, transient absorption experiments shed light onto electron-transfer processes taking place in the ground state and upon photoexcitation. In fact, porphyrin excitation powers an electron transfer to the fullerene yielding charge separated state lifetimes in the nanosecond regime.
authors.affiliation: Institute of Chemical Research of Catalonia , Avgda. Països Catalans 16, 43007 Tarragona, Spain.
authors.forename: Rafael M Krick
authors.initials: RM
authors.lastname: Calderon
authors.forename: Julián
authors.initials: J
authors.lastname: Valero
authors.forename: Bruno
authors.initials: B
authors.lastname: Grimm
authors.forename: Javier
authors.initials: J
authors.lastname: de Mendoza
authors.forename: Dirk M
authors.initials: DM
authors.lastname: Guldi