C-C bonded porous polymers

作者: 时间:2019-03-12 点击数:

报告人:Cafer T. Yavuz






Porous polymers with robust, C-C bonded frameworks offer stability, reproducibility and tunability. Early examples were hypercrosslinked polymer networks by Vadim Davankov in the 1990s. The random connectivity was later replaced by C-C coupling reactions of 3D monomers, in examples such as PAF-1. Although remarkably high surface areas are achieved, we recently revealed that metals and ligands get trapped inside the super structure and could be used to facilitate catalytic transformations. For metal free coupling chemistry, we turned to a rather unknown Reutov reaction where catalytic amount of fluorides deprotect silylated alkynes and lead into SNAr additions to form frameworks structures with C-C bonded networks. This also allowed easy post-modification of the porous polymers. Another versatile path for C-C bonded porous polymers is the condensation reactions. In that, we coupled acetonitrile extensions of aromatic building blocks with rigid multi-aldehydes. The products readily dehydrated and formed fluorescent porous networks. In a separate effort, we used radical initiation to tap into morphology control of crosslinked divinylbenzene. The hollow microspheres proved useful in CO2 capture and gold recovery from e-waste. And lastly, we studied inexpensive Davankov type networks using widely available connectors. The porous polymers showed excellent methane uptake at high pressures. The only drawback for C-C bonded porous polymers is their amorphous nature and our attempts to install order has largely failed. The quest is still open and if successful, they could revolutionize study of confined chemistry in porous materials.

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