MechanochemicallyDriven C–C Bond Formationvia Cu-Complex-Functionalized Polyoxoniobate under Solvent-Free Conditions

Developing a mechanochemical, solvent-free approach for forming C–C bonds in place of traditional solvent-based synthesis is significant for green chemistry. Herein, a novel Cu-complex-functionalized polyoxoniobate-based hybrid material [Cu(tpy)₂]{[Cu(tpy)(H₂O)]₂[Nb₁₀O₂₈]}·5.5H₂O (<b>1</b>, tpy = 2,2′:6′,2″-terpyridine) is successfully synthesized and thoroughly characterized. <b>1</b> displays excellent thermal and solvent stability and is highly mechanical force tolerant. Catalytic studies reveal that <b>1</b> can catalyze the Knoevenagel condensations of a series of aromatic aldehydes with malononitrile to build C–C bond compounds under mechanochemical ball milling conditions. The catalytic system is conducted with no additional heating, with a lower oscillating frequency, and without a solvent. The remarkable performance of catalyst <b>1</b> can be attributed to two factors: one is the sufficient contact between the catalyst and reagents facilitated by mechanical force, as well as the preactivated catalyst by it; the other is the synergistic effect of the Lewis acid–base sites (Cu²⁺ and [Nb₁₀O₂₈]^6–) within the catalyst. The catalyst exhibits outstanding recyclability and can be applied to gram-scale reactions. To the best of our knowledge, this work represents the first example of a mechanochemically driven solvent-free organic transformation using a polyoxometalate-based catalyst.