BULK SYNTHESIS OF 2-DIMENSIONAL POLYMERS - THE MOLECULAR RECOGNITION APPROACH

This manuscript describes the bulk synthesis of shape persistent two-d imensional (2D) polymers using the self-assembly of rigid precursor mo lecules into bilayers. A precursor was synthesized with a structure th at encodes for the necessary molecular recognition events to form bila yers with internal orientational order. These events include homochira l interactions and confine reactive functions to planes leading to cov alent stitching of flat polymers. The resulting molecular objects have a monodisperse thickness of 5 nm and polydisperse planar dimensions o n the order of hundreds or thousands of nanometers. One of the stichin g reactions, the oligomerization of acrylate groups to form an all-car bon backbone, is catalyzed by the presence of dipolar stereocenters 13 atoms away from the double bond. These enantiomerically enriched ster eocenters are substituted by nitrile groups which react to generate th e second stitching backbone of the plate-shaped molecules. A computer simulation indicates that 2D polymers of molar mass in the range of mi llions can be formed with extremely short stitching backbones provided planar confinement of functions is achieved by molecular recognition events. ''Bulk'' syntheses of shape persistent 2D polymers which do no t require external boundaries to confine monomers into 2D spaces may l ead to many interesting advanced materials.