title: Step-by-step self-assembled hybrids that feature control over energy and charge transfer.
abstract: In the current work, we have documented the use of two complementary supramolecular motifs, namely multipoint hydrogen bonding and metal complexation, as a means to control the step-by-step assembly of a panchromatically absorbing and highly versatile solar energy conversion system. On one hand, two different perylenediimides (1a/1b) have been integrated together with a metalloporphyrin (2) by means of the Hamilton receptor/cyanuric acid hydrogen bonding motif into energy transduction systems 1a•2 or 1b•2. Steady-state and time-resolved measurements corroborated that upon selective photoexcitation of the perylenediimides (1a/1b), an energy transfer evolved from the singlet excited state of the perylenediimides (1a/1b) to that of the metalloporphyrin (2). On the other hand, fullerene (3) and metalloporphyrin (2) form the electron donor-acceptor system 2•3 via axial complexation. Photophysical measurements confirm that an electron transfer prevails from the singlet excited state of 2 to the electron-accepting 3. The correspondingly formed radical ion pair state decays with a lifetime of 1.0 ± 0.1 ns. As a complement to the aforementioned, the energy transduction features of 1a•2 were combined with the electron donor-acceptor characteristics of 2•3 to afford 1a•2•3. To this end, time-resolved measurements reveal that the initially occurring energy-transfer interaction (53 ± 3 ps) between 1a/1b and 2 is followed by an electron transfer (12 ± 1 ps) from 2 to 3. From multiwavelength analyses, the lifetime of the radical ion pair state in 1a•2•3-as a product of a cascade of light-induced energy and electron transfer-was derived as 3.8 ± 0.2 ns.
authors.affiliation: Department of Chemistry and Pharmacy, Friedrich-Alexander-Universität Erlangen-Nürnberg, Erlangen, Germany.
authors.forename: Bruno
authors.initials: B
authors.lastname: Grimm
authors.forename: Julia
authors.initials: J
authors.lastname: Schornbaum
authors.forename: Hannelore
authors.initials: H
authors.lastname: Jasch
authors.forename: Olga
authors.initials: O
authors.lastname: Trukhina
authors.forename: Florian
authors.initials: F
authors.lastname: Wessendorf
authors.forename: Andreas
authors.initials: A
authors.lastname: Hirsch
authors.forename: Tomas
authors.initials: T
authors.lastname: Torres
authors.forename: Dirk M
authors.initials: DM
authors.lastname: Guldi
mesh_terms: D004579:Electron Transport; D008665:Metalloporphyrins / Q000737:chemistry*; D055668:Photochemical Processes
chemical_list: D008665:Metalloporphyrins