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

revised on 13.12.2018, 15:20 and posted on 13.12.2018, 17:47 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.


National Institute of General Medical Sciences (8 P20 GM103499)

National Center for Research Resources (5 P20 RR016461)


Email Address of Submitting Author


University of South Carolina Aiken


United States of America

ORCID For Submitting Author


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.