Rational Design and Synthesis of Porous Polymer Networks: Toward High Surface Area
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Head-on polymerization of tetrahedral monomers inherently imparts interconnected diamond cages to the resulting framework with each strut widely exposed. We have designed and synthesized a series of 3,3,5,5- tetraethynylbiphenyl monomers, in which the two phenyl rings are progressively locked into a nearly perpendicular position by adding substituents of different size at 2, 2, 6, and 6 positions, as evident from single crystal structures. Computational simulation suggests that these monomers, though not perfectly regular tetrahedra, could still be self-polymerized into three-dimensional frameworks with the same topology. Indeed, five porous polymer networks (PPNs) have been successfully synthesized with these newly designed monomers through Cu(II)-promoted Eglinton homocoupling reaction. Among them, PPN-13 shows exceptionally high Brunauer-Emmett-Teller (BET) surface area of 3420 m2/g. The total hydrogen uptake is 52 mg/g at 40 bar and 77 K, and the total methane uptake is 179 mg/g at 65 bar and 298 K. 2014 American Chemical Society.
author list (cited authors)
Lu, W., Wei, Z., Yuan, D., Tian, J., Fordham, S., & Zhou, H.
complete list of authors
Lu, Weigang||Wei, Zhangwen||Yuan, Daqiang||Tian, Jian||Fordham, Stephen||Zhou, Hong-Cai