Optical Waveguide and Photoluminescent Polarization in Organic Cocrystal Polymorphs

Organic cocrystals whose unique polymorphic feature can provide a feasible way to investigate and understand the relationship between luminescence properties and aggregate structures have attracted increasing attention in the area of organic optoelectronics. Herein, we prepare polymorphic cocrystals (C1, C2) by using 9,10-bis­((E)-2-(pyridin-3-yl)­vinyl)­anthracene (BP3VA) as chromophore and 1,3,5-trifluoro-2,4,6-triiodobenzene (FIB) as conformer. Both C1 and C2 stack with segregated stacking form, but different intermolecular interactions promote the formation of sheet cocrystals C1 and needle cocrystals C2. C1 exhibits anisotropic optical waveguide property and photoluminescent polarization, while C2 only exhibits the quasi-one-dimensional optical waveguide property. The different optical properties originate from the varieties of molecular packing modes and directions of the optical transition dipole in the two polymorphic cocrystals, which can be clarified through the structure analysis and theoretical calculation. The study can provide a deep understanding of the structure–property relationship of cocrystals and benefit the rational design of novel functional materials.