Stereoselective gridization and polygridization with centrosymmetric molecular packing

The gridarenes, with well-defined edges and vertices, represent versatile nanoscale building blocks for the installation of frameworks and architectures but suffer from difficulty in stereoselective control during their synthesis. Here we report a diastereoselective gridization of superelectrophilic diazafluorene-containing substrates (A(m)B(n)) with crescent shapes into Drawing Hands grids (DHGs). The meso-selectivity reaches 75.6% diastereomeric excess (de) during the gridization of A(1)B(1)-type substrates and maintains ~80% de during the polygridization of A(2)B(2)-type monomers. Such stereocontrol originates from the centrosymmetric molecular packing of two charge-delocalized superelectrophiles with synergistically π–π stacking attractions and coulombic repulsions. As meso-stereoregular structures show 20∼30 nm in length, the rigid ring/chain-alternating polygrids have a Mark–Houwink exponent of 1.651 and a molecular weight (M) dependence of the hydrodynamic radius R(h) ∼ M(1.13). Via the simulation of chain collapse, meso-configured polygridarenes still adopt rod-like conformations that facilitate the high rigidity of organic nanopolymers, distinguished from toroid backbones of rac-type polygrids.