Regulating the catalytic activity of multi-Ru-bridged polyoxometalates based on differential active site environments with six-coordinate geometry and five-coordinate geometry transitions

Five-coordinate geometry around ruthenium with highly exposed active sites has attracted intensive scientific interest due to its superior properties and extensive applications. Herein, we report a series of structurally controllable multi-Ru-bridged polyoxometalates, K5NaH10[{Ru-4(H2O)(n)}(WO2)(4)(AsW9O33)(4)]center dot mH(2)O {1, 1-dehyd-373K, 1-dehyd-473K, 1-dehyd-573K; n = 4, m = 36; n = 4, m = 6; n = 4, m = 0; n = 0, m = 0} fabricated through a feasible assembly strategy using arsenotungstate {2, KNa12H17Cl2(As4W40O140)center dot 29H(2)O} as a structure-directing unit. Systematic characterization methods identified that the six-coordinate geometry can successfully transform into five-coordinate geometry about active sites (Ru) by removing aqua ligands under high reaction temperatures. All the multi-Ru-bridged polyoxometalates demonstrated strong stability and catalytic effectiveness in the transformation of 1-(4-chlorophenyl)ethanol to 4 '-chloroacetophenone under very mild conditions. 1-dehyd-573K, specifically, achieves the best catalytic effectiveness with a turnover frequency (TOF) = 25 100 center dot h(-1) owing to its unique five-coordinate geometry on the Ru sites. To our knowledge, 1-dehyd-573K outperforms other POM-based catalysts in the oxidative catalysis of 1-(4-chlorophenyl)ethanol. The heterogeneous polyoxometalates were also proven to be strongly reusable, with their structural integrities well maintained after multiple-cycle catalytic reactions.