Luminescent Polymorphic Co-crystals: A Promising Way to the Diversity of Molecular Assembly, Fluorescence Polarization, and Optical Waveguide.

The design of molecular optoelectronic materials based on fabricating polymorphs and/or co-crystals has received much recent attention in the fields of luminescence, sensors, nonlinear optics, and so on. If the advantages of the two crystal engineering strategies above were combined, the diversity of self-assembly fashions and the tuning of photofunctional performances would be largely extended. However, such multicomponent examples have still been very limited to date. Herein, we report the construction of luminescent polymorphic co-crystals by assembly of tris(pentafluorophenyl)borane (TPFB) with 9,10-dicyanoanthracene (DCA) and acridine (AC) as paradigms. Different stacking modes and arrangement styles based on identical building block units in polymorphic co-crystals result in adjustable crystalline morphologies and variant photophysical properties (such as fluorescence wavelength, lifetimes, and up-conversion luminescence). The optimized photoluminescence quantum yield (63.1%) and lifetime (57.1 ns) are much higher than those of the pristine assembled units. In addition, two polymorphic co-crystals (DCA@TPFB-1 and AC@TPFB-2) present prominent fluorescence polarization and optical waveguide behaviors due to the highly regulated molecular orientation. Their high one-dimensional luminescence anisotropy (0.652) and low optical waveguide loss (0.0079 dB/μm) outperform most state-of-the-art low-dimensional molecular systems and thus endow them with great opportunities for photonic materials and devices. Therefore, this work not only confirms that constructing polymorphic co-crystals can be an effective way to design new photofunctional materials for luminescence and photonic applications but also discloses a deep understanding on the relationship between variant self-assembled fashions and tunable photofunctional properties of new TPFB-based molecular materials.