Polythiophene Doping of the Cu-Based Metal–Organic Framework (MOF) HKUST-1 Using Innate MOF-Initiated Oxidative Polymerization,Inorganic Chemistry

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Polythiophene Doping of the Cu-Based Metal–Organic Framework (MOF) HKUST-1 Using Innate MOF-Initiated Oxidative Polymerization
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2019-04-05 00:00:00 , DOI: 10.1021/acs.inorgchem.8b03465
Nicholas Marshall ₁ , William James ₁ , Jeremy Fulmer ₁ , Scott Crittenden ₂ , Anthony B. Thompson ₃ , Patrick A. Ward ₃ , Gerard T. Rowe ₁

Affiliation

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, N₂ 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.

中文翻译：

铜基金属有机骨架（MOF）HKUST-1的聚噻吩掺杂，采用先天MOF引发的氧化聚合

铜基金属有机框架（MOF）HKUST-1将有机分子吸附到其孔中。当负载有富电子的低聚噻吩时，所得系统在加热下反应以引发氧化聚合反应，而无需使用任何其他氧化剂或催化剂。在非氧化还原活性的MOF MIL-100（Al）中未观察到此反应。我们已经通过光学和纳米显微镜，振动和紫外可见光谱，X射线光电子能谱，N ₂对复合材料进行了表征。吸附分析和热重分析/残留气体分析。未取代的低聚噻吩在MOF孔内聚合，而3,4-乙二氧基噻吩在MOF表面形成涂层。具有共轭聚合物掺杂剂的MOF复合物被困在其孔中，其复合电子结构发生了深刻的变化。基于与单体结合的HKUST-1模型系统的时变密度泛函理论计算的推理，我们合理化了所观察到的反应性，并提出了一种基于配体-金属电荷转移状态的引发机理。

更新日期：2019-04-05

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