Department of Chemistry, Waterloo Institute for Nanotechnology, University of Waterloo, 200 University Ave. W., Waterloo, Ontario, N2L 3G1, Canada Email: derek.schipper@uwaterloo.ca
› Author AffiliationsWe thank NSERC, the University of Waterloo, and the Canada Foundation for Innovation and the Canada Research Chairs Program (CRC-Tier II, D.J.S.) for financial support. S.S. thanks the Government of Ontario for an Ontario Graduate Scholarship. L.V. thanks NSERC for a postgraduate scholarship. A.J.K thanks NSERC for an undergraduate research student award.
Organic electronics has developed into a significant field of research and industry in the last decade. The progress has been enabled by the many advancements made in synthetic technologies, which allow for the design of a plethora of interesting material candidates. Poly(p-phenylenevinylene) derivatives (PPVs) are a particularly interesting class of polymers that were among the first to garner attention. However, due to their demanding syntheses, limited scope, and relative intolerance to heterocycles, PPVs have fallen out of popularity. New synthetic methods, such as direct C–H bond activation, have emerged that allow for the creation of polyheteroaromatics through the use of simpler starting materials than those used in traditional cross-coupling strategies. Here, we report an extension of a hydroarylation reaction to the synthesis of poly(heteroarylenevinylene) derivatives (PHAVs) containing various desirable heterocycles with Mn values ranging from 8 to 23 kDa without producing stoichiometric amounts of waste.
24Poly[6-(dec-1-yn-1-yl)-N,N-dimethyl-1H-indole-1-carboxamide] (2): To a microwave vial was added indole (1; 64.9 mg, 0.200 mmol), cesium pivalate (2.3 mg, 0.01 mmol), pivalic acid (204 mg, 2.00 mmol), and tetrahydrofuran (0.8 mL). To the stirred solution was added tris(acetonitrile)pentamethylcyclopentadienylrhodium(III) hexafluoroantimonate (4.16 mg, 0.005 mmol), the vial was sealed, and the solution was heated to 110 °C. After four hours, additional tris(acetonitrile)pentamethylcyclopentadienylrhodium(III) hexafluoroantimonate (4.16 mg, 0.005 mmol) was added and the reaction vessel was resealed. After three hours, the polymer was precipitated by pouring the reaction mixture into methanol and isolated by filtration. Polymers with weights of Mn = 34 kDa and Mw = 43 kDa were obtained. 1H NMR (300 MHz, CDCl3, 7.26 ppm): δ = 7.55 (d, J = 8.2 Hz, 1 H), 7.37 (br., 1 H), 7.15 (d, J = 8.0 Hz, 1 H), 6.85 (br., 1 H), 6.67 (br., 1 H), 3.40–2.60 (m, 8 H), 1.75–1.20 (m, 12 H), 0.92 (br., 3 H).
25a
Wang X,
Lane BS,
Sames D.
J. Am. Chem. Soc. 2005; 127: 4996
26Poly[2-((E)-1-(4-((Z)-dodec-1-en-1-yl)phenyl)dodec-1-en-2-yl)-N1,N1,N1′,N1′-tetramethyl-1H,1′H-[6,6′-biindole]-1,1′-dicarboxamide] (3): To a microwave vial, the biindole (0.10 mmol), the dialkyne (0.10 mmol), cesium pivalate (0.01 mmol), and pivalic acid (1.00 mmol) were dissolved in tetrahydrofuran (0.8 mL). To the stirred solution, tris(acetonitrile)pentamethylcyclopentadienylrhodium(III) hexafluoroantimonate (0.01 mmol) was added, the vial was sealed, and the solution was heated to 110 °C in an oil bath. After 22 hours or once the solution became too viscous to stir, the reaction mixture was poured into stirring methanol and the precipitating polymer fibers were collected by vacuum filtration. Polymers with weights of Mn = 23 kDa and Mw = 37 kDa were obtained. 1H NMR (300 MHz, CDCl3, 7.26 ppm): δ = 7.64 (br. m), 7.51 (br. m), 7.36 (br. s), 6.76 (br. s), 6.71 (br. s), 3.30–2.60 (br.), 1.70–1.35 (br.), 1.26 (br. s), 0.90–0.80 (br. m)
27a
Nketia-Yawson B,
Lee H.-S,
Seo D,
Yoon Y,
Park W.-T,
Kwak K,
Son HJ,
Kim B,
Noh Y.-Y.
Adv. Mater. 2015; 27: 3045
