We
report a multi-component synthetic strategy on a two-dimensional
crystalline covalent organic framework (COF) by connecting acetonitrile
with aromatic aldehyde and acetaldehyde moieties to form an unprecedented
cyano-substituted buta-1,3-diene linkage. Different from most of the
COFs that were crystallized from the condensations from two components,
the presented COF is generated from two competitive and reversible
reactions among three moieties. The buta-1,3-diene COF exhibits remarkable
photoactivity with a low exciton binding energy of 44.4 ± 1.5
meV for promoted charge separation, which enables the buta-1,3-diene-linked
COF as an efficient photocatalyst for various aerobic oxidation reactions
under visible light. Our multi-component synthesis strategy may provide
new sights for synthesizing COFs with structural diversity and functional
variability that are hard to achieve by traditional COF synthesis.