Non-covalent Supramolecular 1D Alternating Copolymer in Crystal toward 2D Anisotropic Photon Transport

To realize organic integrated optoelectronic circuits, there is a need for anisotropic optical waveguides at the micro/nanoscale. Anisotropic alignment of one-dimensional (1D)-ordered supramolecular structures composed of light-emissive π-conjugated molecules in a crystal may meet the requirements of such waveguides. Here, we designed a bipyridyl-appended acrylonitrile-based π-conjugated molecule 1, which produced a 1D supramolecular polymer constructed through non-covalent bonding between a lone pair in 1 and a σ-hole in 1,4-diiodo-2,3,5,6-tetrafluorobenzene 2. The 1D copolymer of 1 and 2 is aligned horizontally with the two-dimensional (2D) crystal surface because of the angle-controlled supramolecular synthons. As a result of control over the non-covalent bonding direction, anisotropic photoluminescence and photon transport (optical waveguiding) characteristics are realized by orienting the transition dipole moment horizontally with respect to the 2D surface. Compared with the loss coefficient αL =52dBcm-1 for the long-axis direction of the 2D platelet cocrystal, a very large difference of αS =2111dBcm-1 is present in the crystal short-axis direction. The anisotropic waveguiding ability, αL/αS, is estimated to be 41, which is more than an order of magnitude greater than previously reported 2D platelet crystal waveguides. This supramolecular synthon provides an approach to designing anisotropic photon transporters and highly regulated optical logic circuits.