Controlling Morphological Dimensions of Organic Charge‐Transfer Cocrystal by Manipulating the Growth Kinetics for Optical Waveguide Applications

Abstract Precise fabrication of organic micro/nanostructures with regular morphology has gained a considerable concern in developing high‐performance optoelectronic devices, which is still a huge challenge to realize tunable morphology without the dependence on molecule packing arrangement. Herein, a thermodynamic/kinetic controlled self‐assembly for triphenylene‐7,7,8,8‐tetracyanoquinodimethane (TP‐TCNQ) cocrystal, with well‐defined microwires and microplates based on the same crystal structure, is proposed. With the low solution concentration of C = 5 mm, the comparable growth rates along [011] driven by π–π interaction and along [100] driven by charge‐transfer (CT) interaction facilitate the formation of thermodynamically favored shape of microplates. In contrast, the prominent CT interaction along [100] leads to the construction of microwires at kinetic state under high‐concentration solution of C = 10 mm. Furthermore, the prepared TP‐TCNQ microwires and microplates demonstrate isotropic photonic transmissions with the low optical loss coefficient of 0.033 and 0.042 dB µm⁻¹, respectively. This strategy provides a novel avenue to finely construct the organic microcrystals with desired morphology for potential optoelectronics.