Multilayered Uranyl-Containing Tungstophosphate with Two Different Dawson Units for the Photocatalytic Oxy-Thiocyanation of Alkynes.

A novel multilayered uranyl-containing tungstophosphate, [H2N(CH3)2]13Na5[(UO2)2(W2O6)2(H2P2W15O54)(H2P2W14O52)]·15H2O (U2P4W33), has been successfully synthesized via an in situ assembly strategy. The compound was composed of three distinct building units, including one trivacant Dawson {P2W15}, one rectangle {U2W4}, and one tetravacant Dawson {P2W14}. Moreover, U2P4W33 exhibits remarkable catalytic activity for the oxy-thiocyanation of terminal alkynes under visible-light irradiation in the presence of oxygen, utilizing ammonium thiocyanate as the thiocyanating reagent. The catalytic system demonstrates broad substrate compatibility, affording a diverse series of α-thiocyanato ketones in excellent yields under mild conditions. This work not only broadens the structural diversity of actinide-containing polyoxometalates but also presents an efficient photocatalytic strategy for the synthesis of valuable α-thiocyanato ketones.