A Light-Responsive Metal–Organic Framework with Perchlorinated Nanographene Ligands
Harnessing water as a sustainable electron source for artificial photosynthesis remains a significant challenge. This work presents <b>Alice-MOF-1</b>, a novel zirconium metal-organic framework (MOF) incorporating hexatopic ligands with a perchlorinated hexa-<i>peri</i>-hexabenzocoronene (HBC) core, as a photocatalyst for CO<sub>2</sub> reduction using water as the terminal electron donor. Contortion of the ligand, induced by edge chlorination, minimizes π-stacking and enhances solubility, enabling direct MOF synthesis. The controlled arrangement of chromophores within <b>Alice-MOF-1</b> is crucial for enabling the complex multielectron redox reactions. The unique ligand architecture within the MOF promotes symmetry-breaking charge transfer (SBCT), a mechanism observed in natural photosynthesis, leading to efficient charge separation with minimal energy loss. Femtosecond transient absorption spectroscopy and time-resolved electron paramagnetic resonance spectroscopy (EPR) confirm the formation of long-lived radical ions, providing direct evidence for efficient SBCT and negligible charge recombination. These findings demonstrate the power of MOF-based chromophore assemblies to mimic nature's light-harvesting strategies for sustainable energy conversion.
Authors
- Peter Zapol (ORCID: https://orcid.org/0000-0003-0570-9169)
- Oleg G. Poluektov (ORCID: https://orcid.org/0000-0003-3067-9272)
- Ksenija D. Glusac (ORCID: https://orcid.org/0000-0002-2734-057X)
- Roushan Prakash Singh (ORCID: https://orcid.org/0000-0001-6279-3040)
- Jens Niklas (ORCID: https://orcid.org/0000-0002-6462-2680)
- Robert F. Klie (ORCID: https://orcid.org/0000-0003-4773-6667)
- Atefeh Nadeali (ORCID: https://orcid.org/0000-0002-9861-7660)
- Haiying He (ORCID: https://orcid.org/0000-0002-3493-2784)
- Jasleen K. Bindra (ORCID: https://orcid.org/0000-0001-7031-7482)
- Danial Zangeneh (ORCID: https://orcid.org/0009-0009-0650-5230)
- Kenneth Brezinsky (ORCID: https://orcid.org/0000-0003-3923-4202)
- Xin Zheng (ORCID: https://orcid.org/0000-0002-5506-8112)
- Brian P. Chaplin (ORCID: https://orcid.org/0000-0003-1668-5414)
- Juan P. Vizuet (ORCID: https://orcid.org/0000-0002-3660-2041)
- Subharaj Hossain (ORCID: https://orcid.org/0000-0002-3125-7226)
- Nikita Gupta (ORCID: https://orcid.org/0000-0003-0398-7317)
Institutions
- Argonne National Laboratory (US)
- Valparaiso University (US)
- University of Illinois Chicago (US)
- Division of Materials Science and Engineering (AU)
Publication Details
- Journal
- Journal of the American Chemical Society
- Published
- 2025-05-05
- DOI
- https://doi.org/10.1021/jacs.5c02844
- Citations
- 8
- Primary Topic
- Metal-Organic Frameworks: Synthesis and Applications
- Type
- article
- Field-Weighted Citation Impact
- 4.30
Funders
- Division of Chemical, Bioengineering, Environmental, and Transport Systems
- Army Research Office
- Argonne National Laboratory