Due to the enormous chemical and structural diversities
and designable
properties and functionalities, covalent organic frameworks (COFs)
hold great promise as tailored materials for industrial applications
in electronics, biology, and energy technologies. They were typically
obtained as partially crystalline materials, although a few single-crystal
three-dimensional (3D) COFs have been obtained recently with structures
probed by diffraction techniques. However, it remains challenging
to grow single-crystal COFs with controlled morphology and to elucidate
the local structures of 3D COFs, imposing severe limitations on the
applications and understanding of the local structure–property
correlations. Herein, we develop a method for designed growth of five
types of single crystalline flakes of 3D COFs with controlled morphology,
front crystal facets, and defined edge structures as well as surface
chemistry using surfactants that can be self-assembled into layered
structures to confine crystal growth in water. The flakes enable direct
observation of local structures including monomer units, pore structure,
edge structure, grain boundary, and lattice distortion of 3D COFs
as well as gradually curved surfaces in kinked but single crystalline
3D COFs with a resolution of up to ∼1.7 Å. In comparison
with flakes of two-dimensional crystals, the synthesized flakes show
much higher chemical, mechanical, and thermal stability.