1D versus 2D cocrystals growth via microspacing in-air sublimation

Organic cocrystals possess valuable properties owing to the synergistic effect of the individual components. However, the growth of molecular cocrystals is still in its primary stage. Here we develop a microspacing in-air sublimation method to grow organic cocrystals, and furthermore to realize morphology control on them, which is essential for structure–property relations. A series of polycyclic aromatic hydrocarbon (PAH)‒1,2,4,5-tetracyanobenzene (TCNB) complexes cocrystals are grown directly on the substrate, with the morphology tunable from 1D needle-like to 2D plate-like on demand. Spatially resolved photoluminescence spectra analyses on different cocrystals display morphology dependent and anisotropic optical waveguiding properties. In situ observation and energy calculations of the crystallization processes reveal the formation mechanism being from a competition between growth kinetics-defined crystal habit and the thermodynamics driving force. This growth technique may serve the future demand for tunable morphology organic cocrystals in different functional applications.