Tricarboxylic-Ligand-Decorated Lanthanoid-Inserted Heteropolyoxometalates Built by Mixed-Heteroatom-Directing Polyoxotungstate Units: Syntheses, Structures, and Electrochemical Sensing for 17β-Estradiol.

Organic-inorganic hybrid metal-oxide clusters have been pursued for many years, benefiting from their abundant structures and prominent performances. Upon our exploration, a family of unusual mixed-heteroatom (Sb, P)-directing lanthanoid (Ln)-inserted heteropolyoxotungstates (Ln-HPOTs), [(CH)NH]NaH[Ln(HP)W(HO)(Hptca)O][SbWO]·27HO [Ln = Ce (), La (), Pr ()], functionalized by 1,2,3-propanetricarboxylic acid (Hptca) was achieved. The intriguing trimeric [Ln(HP)W(HO)(Hptca)O][SbWO] polyanion was established by two trivacant [B-α-SbWO] segments mounted on both sides and one rare [HPWO] segment at the bottom, which are bridged via an organic-inorganic hybrid [WLn(HO)O(Hptca)] central moiety.