Symmetry-Guided Synthesis of N,N′-Bicarbazole and Porphyrin-Based Mixed-Ligand Metal–Organic Frameworks: Light Harvesting and Energy Transfer

Authors

Christian Fiankor, University of Nebraska - Lincoln
James Nayakuchena, Marquette University
Rebecca Shu Hui Khoo, Lawrence Berkeley National Laboratory
Xu Zhang, Huaiyin Normal University
Yuchen Hu, University of Nebraska − Lincoln
Sizhuo Yang, Marquette University
Jier Huang, Marquette UniversityFollow
Jian Zhang, Lawrence Berkeley National Laboratory

Document Type

Article

Publication Date

12-8-2021

Publisher

American Chemical Society

Source Publication

Journal of the American Chemical Society

Source ISSN

0002-7863

Original Item ID

DOI: 10.1021/jacs.1c10291

Abstract

In the past decades, many attempts have been made to mimic the energy transfer (EnT) in photosynthesis, a key process occurring in nature that is of fundamental significance in solar fuels and sustainable energy. Metal–organic frameworks (MOFs), an emerging class of porous crystalline materials self-assembled from organic linkers and metal or metal cluster nodes, offer an ideal platform for the exploration of directional EnT phenomena. However, placing energy donor and acceptor moieties within the same framework with an atomistic precision appears to be a major synthesis challenge. In this work, we report the design and synthesis of a highly porous and photoactive N,N′-bicarbazole- and porphyrin-based mixed-ligand MOF, namely, NPF-500-H₂TCPP (NPF = Nebraska porous framework; H₂TCPP = meso-tetrakis(4-carboxyphenyl)porphyrin), where the secondary ligand H₂TCPP is incorporated precisely through the open metal sites of the equatorial plane of the octahedron cage resulting from the underlying (4,8) connected network of NPF-500. The efficient EnT process from N,N′-bicarbazole to porphyrin in NPF-500-H₂TCPP was captured by time-resolved spectroscopy and exemplified by photocatalytic oxidation of thioanisole. These results demonstrate not only the capability of NPF-500 as the scaffold to precisely arrange the donor–acceptor assembly for the EnT process but also the potential to directly utilize the EnT process for photocatalytic applications.

Comments

Accepted version. Journal of the American Chemical Society, Vol. 143, No. 43 (December 8, 2021): 20411-20418. DOI. © 2021 American Chemical Society. Used with permission.

Recommended Citation

Fiankor, Christian; Nayakuchena, James; Khoo, Rebecca Shu Hui; Zhang, Xu; Hu, Yuchen; Yang, Sizhuo; Huang, Jier; and Zhang, Jian, "Symmetry-Guided Synthesis of N,N′-Bicarbazole and Porphyrin-Based Mixed-Ligand Metal–Organic Frameworks: Light Harvesting and Energy Transfer" (2021). Chemistry Faculty Research and Publications. 1041.
https://epublications.marquette.edu/chem_fac/1041