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Polythiophene Doping of Metal-Organic Frameworks Using Innate MOF-Catalyzed Oxidative Polymerization

preprint
revised on 13.12.2018 and posted on 13.12.2018 by Nicholas Marshall, William James, Jeremy Fulmer, Scott Crittenden, Gerard T. Rowe
The copper- and iron-containing metal-organic frameworks
(MOFs) HKUST-1 and MIL-100(Fe) absorb organic molecules into their pores. When loaded with electron-rich oligothiophenes, these MOFs react under heat to initiate oxidative polymerization of entrapped monomers. This reaction is not observed in the non-redox-active MOF MIL-100(Al). The resulting MOF composites contain conjugated polymer dopants trapped inside their pores, causing profound shifts in the composite electronic structure. We have characterized the composites by infrared, Raman, and UV-visible spectroscopy and examined their structure using confocal microscopy, scanning electron microscopy, and atomic force microscopy. Reasoning from TD-DFT calculations of an HKUST-1 model system bound to monomers, we rationalize the observed reactivity and propose an initiation mechanism based on a ligand-to-metal charge transfer state.

Funding

National Institute of General Medical Sciences (8 P20 GM103499)

National Center for Research Resources (5 P20 RR016461)

History

Email Address of Submitting Author

nicholasm@usca.edu

Institution

University of South Carolina Aiken

Country

United States of America

ORCID For Submitting Author

0000-0001-8048-0857

Declaration of Conflict of Interest

The authors declare no conflicting interests.

Version Notes

ChemRxiv version 4 of this manuscript has had data added, including reflectance UV, MALDI-TOF spectra of composites and HKUST-1, and PXRD data.

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