Two Organic–Inorganic Hybrid 3D {P 5 W 30 }‐Based Heteropolyoxotungstates with Transition‐Metal/Ln–Carboxylate–Ln Connectors

Two unique organic–inorganic hybrid polyoxometalates constructed from Preyssler‐type [Na(H 2 O)P 5 W 30 O 110 ] 14− ({P 5 W 30 }) subunits and TM/Ln–carboxylate–Ln connectors (TM=transition metal, Ln=lanthanide), KNa 7 [{Sm 6 Mn(μ‐H 2 O) 2 (OCH 2 COO) 7 (H 2 O) 18 }{Na(H 2 O)P 5 W 30 O 110 }] ⋅ 22 H 2 O ( 1 ) and K 4 [{Sm 4 Cu 2 (gly) 2 (ox)(H 2 O) 24 }{NaP 5 W 30 O 110 }]Cl 2 ⋅ 25 H 2 O ( 2 ; gly=glycine, ox=oxalate) have been hydrothermally synthesized and characterized by elemental analyses, IR spectra, UV/Vis‐NIR spectra, thermogravimetric analyses, power X‐ray diffraction, and single‐crystal X‐ray diffraction. Compound 1 displays one interesting 3D framework built by three types of subunits, {P 5 W 30 }, [Sm 2 Mn(μ‐H 2 O) 2 (OCH 2 COO) 2 (H 2 O) 5 ] 4+ , and [Sm 4 (OCH 2 COO) 5 (H 2 O) 13 ] 2+ , whereas 2 also manifests the other intriguing 3D architecture created by three types of subunits, {P 5 W 30 }, [SmCu(gly)(H 2 O) 8 ] 4+ , and [Sm 2 (ox)(H 2 O) 8 ] 4+ . To our knowledge, 1 and 2 are the first 3D frameworks that contain {P 5 W 30 } units and TM/Ln–carboxylate–Ln connectors. The fluorescent properties of 1 and 2 have been investigated.