Supramolecular Fullerene Tetramers Concocted with Porphyrin Boxes Enable Efficient Charge Separation and Delocalization
- 24 June 2020
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 142 (29), 12596-12601
- https://doi.org/10.1021/jacs.0c05339
Abstract
Herein, we report a novel porphyrin/fullerene supramolecular cocrystal using a shape-persistent zinc-metalated porphyrin box (Zn-PB) and C60/C70. An unprecedented arrangement of a tightly packed square-planar core of four C60 or C70 surrounded by six cube-shaped Zn-PBs was observed. This unique packing promotes strong charge transfer (CT) interactions between the two components in the ground state and formation of charge-separated states with very long lifetimes in the excited state and enables unusually high photoconductivity. Quantum chemical calculations show that these features are enabled by delocalized orbitals that promote the CT, on one hand, and that are spatially separated from each other, on the other hand. This work may open a new avenue to design novel electron donor/acceptor architectures for artificial photosynthesis.Keywords
Funding Information
- Deutsche Forschungsgemeinschaft (182849149-SFB 953)
- Japan Society for the Promotion of Science (19F19044, 26102011)
- Institute for Basic Science (IBS-R007-D1, IBS-R10-A1)
This publication has 33 references indexed in Scilit:
- Organic crystalline materials in flexible electronicsChemical Society Reviews, 2018
- Organic Donor–Acceptor Complexes as Novel Organic SemiconductorsAccounts of Chemical Research, 2017
- Long-Lived Charge Separation and Applications in Artificial PhotosynthesisAccounts of Chemical Research, 2014
- Towards artificial photosynthesis: Supramolecular, donor–acceptor, porphyrin- and phthalocyanine/carbon nanostructure ensemblesCoordination Chemistry Reviews, 2012
- Room-temperature ferroelectricity in supramolecular networks of charge-transfer complexesNature, 2012
- Self-Assembly Strategies for Integrating Light Harvesting and Charge Separation in Artificial Photosynthetic SystemsAccounts of Chemical Research, 2009
- Curves ahead: molecular receptors for fullerenes based on concave–convex complementarityChemical Society Reviews, 2008
- Fullerene−Porphyrin ConstructsAccounts of Chemical Research, 2004
- Fullerene–porphyrin architectures; photosynthetic antenna and reaction center modelsChemical Society Reviews, 2001
- Structural chemistry of supramolecular assemblies that place flat molecular surfaces around the curved exteriors of fullerenesCoordination Chemistry Reviews, 1999