Construction of Clathrochelate-Bridged Covalent Organic Frameworks via Coordinate and Covalent Bonding

we establish a synergistic co-assembly strategy integrating metal-ligand coordination with dynamic covalent B−O−N linkages for one-pot synthesis of a three-dimensional clathrochelate-bridged COF (Fe-CC-COF). Using an oxime ligand, FeCl2, and a tetrahedral boronate under kinetically synchronized conditions, we achieved high crystallinity and porosity. X-ray absorption fine structure (XAFS) spectroscopy confirmed well-defined FeN6 coordination. The framework exhibits reversible transitions between chelate-linked and metal-cage configurations and allows post-synthetic incorporation of diverse metal ions (M = Co2+, Ni2+, Cu2+, Zn2+), expanding the M-CC-COF family.