Structural Dynamism-Actuated Reversible CO₂ Adsorption Switch and Postmetalation-Induced Visible Light C_α–H Photocyanation with Rare Size Selectivity in N-Functionalized 3D Covalent Organic Framework

The impact of dimensionality and flexibility on anticipated properties has prompted major research focus to three-dimensional covalent organic frameworks (3D COFs), where astute functionalization of porous channels for dynamic CO2 adsorption as well as size-exclusive C–H activation under eco-friendly condition are the most intriguing advanced applications. Herein, we report an imine-based, diamondoid COF that embraces one-dimensional porous channels in spite of ninefold interpenetration. A combination of intrinsic microporosity and pore wall decoration with accessible N atoms from linear strut renders this 3D COF display reasonable CO2 affinity with decent selectivity (CO2/N2: 64.2; CO2/CH4: 10.5) alongside worthy multicyclic CO2 uptake–release recurrence. Interestingly, the COF undergoes solvent-assisted alteration to a pore-stretched structure via −C═N– “pedal” motion with a concomitant enhancement in CO2 uptake, where steady reversibility of such structural dynamism instigates unprecedented CO2 adsorption switch up to seven consecutive cycles. Integration of 2,2′-bipyridyl units benefits anchoring of homogeneous catalyst to device first-ever Ru(Bpy)22+ hooked diamondoid COF (Ru-COF), which performs visible-light-triggered oxidative cyanation of tertiary amines at room temperature, using molecular oxygen as a selective oxidant in green solvent H2O. The photocatalyst-engineered COF manifests excellent recyclability and comparable activity to that of homogeneous catalyst. To the best of Ru-COF, atom-economic photocyanation is realized via in situ generated iminium ion, wherein larger-sized substrates exhibit insignificant conversion of α-aminonitriles and validate rarest size selectivity in oxidative Strecker reaction. This study not only demonstrates potential of 3D COF as next-generation dynamic CO2 adsorbent but also sheds light on tailor-made fabrication of smart functional material for promising catalytic applications through an environmentally benign route.