Oxidative polymerization of terthiophene and a substituted thiophene monomer in metal-organic framework thin films

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

“…The excited state produced by the transition effectively constitutes a radical cation centered on the oligothiophene monomer, (Figure 15) a reactive intermediate which will initiate polymerization similarly to well-known processes initiated by oxidizing agents such as persulfates or ferric chloride. 26,42 The trend in the vertical excitation energies in the present study (decreasing by 0.98 eV from thiophene to bithiophene) show a reasonable similarity to reported vertical ionization potential differences between thiophene and bithiophene performed at a comparable level of theory, which ranged from 1.3 eV in the gas phase to 0.7 eV using a PCM model of acetonitrile. 43…”

“…Several other groups prepared PPy/MOF composites by direct reaction between pyrrole and MOFs in the presence of oxygen. Haldar et al have also very recently reported a conjugated polymer/MOF composite in thin film form, 26 and Qiu et al used HKUST-1 as a template for electropolymerization of aniline. 27 As we set out to develop our own techniques for MOF/PT hybrid preparation, we stumbled upon an exciting discovery; the Cu(II)-based MOF HKUST-1 can induce oxidative polymerization of oligothiophenes innately, without the application of an external oxidant such as ferric chloride or iodine.…”

Direct grafting-from of PEDOT from a photoreactive Zr-based MOF – a novel route to electrically conductive composite materials

“…The rare examples rely on the formation of p-stacked pathways through threedimensional MOFs, 30,31 delocalization in two-dimensional coordination polymers [32][33][34][35][36] or via sulfur-based linker molecules 37 as well as the special properties of iron-based MOFs. [38][39][40] Alternatively, the introduction of guest molecules like tetracyanoquinododimethane, 41 fullerene, 42 polyaniline and polythiophene derivatives, 40,[43][44][45][46][47][48][49] as well as the formation of composites with conducting carbon modifications 42,[50][51][52][53][54] or conducting polymers 55,56 can lead to conductive MOF-based materials. Generally, the introduction of guests into the pore space can compromise porosity; on the contrary, polymerization of EDOT in the pore system of MIL-101(Cr) leads to a conductive material with only slightly reduced porosity.…”

Co-Oligomerization of Electroconductive Monomers in a Cyclodextrin-Based Metal–Organic Framework

“…No further polymerization proceeds because of the hydrophobic nanopores located between the hydrophilic nanopores. Oxidative polymerization of EDOT in a metal-organic framework (MOF) has been investigated for MIL-101 (Cr) (Le Ouay et al, 2016) with pentagonal and hexagonal windows, and for surface adsorbed MOF thin lms (SURMOF) of Cu(dbc) and Zn(pbdc) with square 1-D channels (Haldar et al, 2018). Oligomers composed of up to nine EDOT units may interact with each other and form loosely packed clusters in the MIL-101(Cr) cavity.…”