期刊
INORGANIC CHEMISTRY
卷 58, 期 9, 页码 5561-5575出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.8b03465
关键词
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资金
- College of Sciences and Engineering Summer Scholars Institute, USC Aiken
- Workforce Opportunities in Regional Careers (WORC) grant
- ADP
- South Carolina IDeA Networks of Biomedical Research (SC INBRE)
- National Center for Research Resources from the National Institutes of Health [5 P20 RR016461]
- National Institute of General Medical Sciences from the National Institutes of Health [8 P20 GM103499]
- RISE grant from the Office of the Vice President for Research, University of South Carolina
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.
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