Three {Bi2W21} Tungstobismuthate Clusters Linked by Acetate‐Stabilized Ln Bridges

The evolution of tungstobismuthate chemistry is currently attracting wide interest due to its unique structural feature. Herein, we report for the first time three novel lanthanide (Ln)‐containing tungstobismuthates Na 6 Li 16 [Pr(H 2 O) 2 (Ac)Bi 2 W 21 O 72 (OH)] 2 · 80H 2 O ( 1 ) and Na 9 Li 13 [Ln(H 2 O)(Ac)Bi 2 W 21 O 72 (OH)] 2 · 74H 2 O (Ln = Gd III ( 2 ), Dy III ( 3 ); HAc = acetic acid) by facile one‐pot self‐assembly method. The 1 – 3 represent the first type architectures from two peculiar [Bi 2 W 21 O 72 (OH)] 13– fragments and one di‐acetate‐chelating [Pr(H 2 O) 2 (Ac)] 2 4+ or [Ln(H 2 O)(Ac)] 2 4+ linkage. Most importantly, the [Bi 2 W 21 O 72 (OH)] 13– fragment contains two tri‐vacant [BiW 9 O 33 ] 9– subunits linked with two internal [WO 2 ] 2+ groups and one external [WO 2 (OH)] + moiety, which is remarkably different from the previously reported one. Photoluminescence (PL) studies reveal that 1 and 3 display the typical emission originated from the corresponding Ln III cations whilst the PL decay lifetime of 3 stems from the common contribution of Dy III ions and [Bi 2 W 21 O 72 (OH)] 13– fragments accompanied by the possible energy transfer from [Bi 2 W 21 O 72 (OH)] 13– fragments to Dy III centers. Magnetic investigation of 3 indicates the potential single‐molecule magnet (SMM) character. This work opens a new avenue for fabrication of Ln‐containing tungstobismuthate materials.