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.