A π-conjugated covalent organic framework enables interlocked nickel/photoredox catalysis for light-harvesting cross-coupling reactions.

Covalent organic frameworks (COFs) are an outstanding platform for heterogeneous photocatalysis. Herein, we synthesized a pyrene-based two-dimensional C[double bond, length as m-dash]C linked π-conjugated COF Knoevenagel condensation and anchored Ni(ii)-centers through bipyridine moieties. Instead of traditional dual metallaphotoredox catalysis, the mono-metal decorated Ni@Bpy-spc-COF interlocked the catalysis mediated by light and the transition metal.

Intermolecular dearomative [4 + 2] cycloaddition of naphthalenes visible-light energy-transfer-catalysis.

The dearomative cycloaddition reaction serves as a blueprint for creating sp-rich three-dimensional molecular topology from flat-aromatic compounds. However, severe reactivity and selectivity issues make this process arduous. Herein, we describe visible-light energy-transfer catalysis for the intermolecular dearomative [4 + 2] cycloaddition reaction of feedstock naphthalene molecules with vinyl benzenes.