Enhanced electronic communication through a conjugated bridge in a porphyrin-fullerene donor-acceptor couple
A ZnP-2EDOTV-C60 triad, with enhanced electronic communication between terminus donor and acceptor moieties, was synthesized and studied both experimentally and theoretically. Electrochemical measurements and density functional theory calculations support that the first oxidation takes place on the 3,4-ethylenedioxythiophenevinylene (2EDOTV) bridge followed by the oxidation of the ZnP moiety at slightly higher energies. The electronic communication between the terminal electron-donor ZnP and the electron-acceptor C60 units is enhanced by the conjugated EDOTV-based spacer leading to photoinduced electron transfer over the distance >2 nm in the picosecond time domain. The involvement of the s…
Role of the bridge in photoinduced electron transfer in porphyrin-fullerene dyads.
The role of π-conjugated molecular bridges in through-space and through-bond electron transfer is studied by comparing two porphyrin-fullerene donor-acceptor (D-A) dyads. One dyad, ZnP-Ph-C60 (ZnP = zinc porphyrin), incorporates a phenyl bridge between D and A and behaves very similarly to analogous dyads studied previously. The second dyad, ZnP-EDOTV-C60, introduces an additional 3,4-ethylenedioxythienylvinylene (EDOTV) unit into the conjugated bridge, which increases the distance between D and A, but, at the same time, provides increased electronic communication between them. Two essential outcomes that result from the introduction of the EDOTV unit in the bridge are as follows: 1) faster…
Self-Assembly-Directed Organization of a Fullerene–Bisporphyrin into Supramolecular Giant Donut Structures for Excited-State Charge Stabilization
Functional materials composed of spontaneously self-assembled electron donor and acceptor entities capable of generating long-lived charge-separated states upon photoillumination are in great demand as they are key in building the next generation of light energy harvesting devices. However, creating such well-defined architectures is challenging due to the intricate molecular design, multistep synthesis, and issues associated in demonstrating long-lived electron transfer. In this study, we have accomplished these tasks and report the synthesis of a new fullerene–bis-Zn-porphyrin e-bisadduct by tether-directed functionalization of C60 via a multistep synthetic protocol. Supramolecular oligom…