Abstract
π-Conjugated polymers are widely used in optoelectronics for fabrication of organic photovoltaic devices, organic light-emitting diodes, organic field effect transistors, and so on. Here we describe the protocol for polycondensation of bifunctional aryl ethers or aryl ammonium salts with aromatic dimetallic compounds through cleavage of inert C–O/C–N bonds. This reaction proceeds smoothly in the presence of commercially available Ni/Pd catalyst under mild conditions, affording the corresponding π-conjugated polymers with high molecular weight. The method is applicable to monomers that are unreactive in other currently employed polymerization procedures, and opens up the possibility of transforming a range of naturally abundant chemicals into useful functional compounds/polymers.
Highlights
On the other hand, aromatic C–O/C–N bonds are ubiquitous in natural products, pharmaceuticals, and functional molecules, and many compounds containing these bonds, such as ethers and anilines, are produced on an industrial scale at reasonable cost
Synthetic transformations via inert aromatic C–O12–17 and/or C–N18 bond cleavage have attracted a great deal of attention, as an alternative to the use of reactive aromatic halides, and as a new methodology for the direct conversion and rapid derivatization of functional molecules containing aromatic C–O/C–N bonds
NiCl2(PCy3)[2] (PCy3: tricyclohexylphosphine) was selected as the catalyst, as it is known to be effective for ethereal C–O bond cleavage[12,13,14,15,16,17,21,22,23,24,25,26,27,28]
Summary
Aromatic C–O/C–N bonds are ubiquitous in natural products, pharmaceuticals, and functional molecules, and many compounds containing these bonds, such as ethers and anilines, are produced on an industrial scale at reasonable cost. Several groups, including ours, have developed various types of cross-coupling reactions of aryl ethers, including Kumada–Tamao–Corriu type (Mg)[22,23,24,25,26,27,28], Suzuki–Miyaura type (B)[29,30,31,32,33,34,35], Negishi type (Zn, Al)[36,37,38,39], Murahashi type (Li)[40,41,42,43], and related C–H44–50 or C–X (X = B, N, Si, etc.)[51,52,53,54,55] bond formation reactions It remains unclear whether such inert ethereal C–O bond cleavage can be extended to synthesize functional polymers. We report polycondensation using aromatic ether or ammonium salt as a monomer for the synthesis of various πconjugated polymers via inert C–O/C–N bond cleavage (Fig. 1)
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