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Polythiophene doping of the cu-based metal-organic framework (MOF) HKUST-1 using innate MOF-initiated oxidative polymerization
Marshall, N., James, W., Fulmer, J., Crittenden, S., Thompson, A. B., Ward, P. A., & Rowe, G. T. (2019). Polythiophene doping of the cu-based metal-organic framework (MOF) HKUST-1 using innate MOF-initiated oxidative polymerization. Inorganic Chemistry, 58(9), 5561-5575. https://doi.org/10.1021/acs.inorgchem.8b03465
The copper-based metal-organic framework (MOF) HKUST-1 adsorbs organic molecules into its pores. When loaded with electron-rich oligothiophenes, the resulting system reacts under heat to initiate oxidative polymerization without the use of any other oxidant or catalyst. This reaction is not observed in the non-redox-active MOF MIL-100(Al). We have characterized the composites by optical and nanoscale microscopy, vibrational and UV-vis spectroscopy, X-ray photoelectron spectroscopy, N-2 sorption analysis, and thermogravimetric analysis/residual gas analysis. Unsubstituted oligothiophenes polymerize within MOF pores, while 3,4-ethylenedioxythiophene forms a coating on the MOF surface. MOF composites with conjugated polymer dopants trapped inside their pores undergo profound shifts in the composite electronic structure. Reasoning from time-dependent density functional theory 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.