Two Organic–Inorganic Hybrid 3D {P₅W₃₀}‐Based Heteropolyoxotungstates with Transition‐Metal/Ln–Carboxylate–Ln Connectors

Abstract

Two unique organic-inorganic hybrid polyoxometalates constructed from Preyssler-type [Na(H2 O)P5 W30 O110 ](14-) ({P5 W30 }) subunits and TM/Ln-carboxylate-Ln connectors (TM=transition metal, Ln=lanthanide), KNa7 [{Sm6 Mn(μ-H2 O)2 (OCH2 COO)7 (H2 O)18 }{Na(H2 O)P5 W30 O110 }]⋅22 H2 O (1) and K4 [{Sm4 Cu2 (gly)2 (ox)(H2 O)24 }{NaP5 W30 O110 }]Cl2 ⋅25 H2 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, {P5 W30 }, [Sm2 Mn(μ-H2 O)2 (OCH2 COO)2 (H2 O)5 ](4+) , and [Sm4 (OCH2 COO)5 (H2 O)13 ](2+) , whereas 2 also manifests the other intriguing 3D architecture created by three types of subunits, {P5 W30 }, [SmCu(gly)(H2 O)8 ](4+) , and [Sm2 (ox)(H2 O)8 ](4+) . To our knowledge, 1 and 2 are the first 3D frameworks that contain {P5 W30 } units and TM/Ln-carboxylate-Ln connectors. The fluorescent properties of 1 and 2 have been investigated.

Four Hybrid Materials Based on Preyssler P5W30 Polyoxometalate and First-Row Transition-Metal Complex

“…The Preyssler P 5 W 30 anion acts as a dodecadentate inorganic ligand that coordinates to 12 Cu­(II) ions directly (Figure a). Although the Preyssler P 5 W 30 anion has a high of 30 oxygen atoms on the surface available to bind to metal centers, its coordination numbers reported are not higher than 13 . Therefore, the dodecadentate Preyssler P 5 W 30 anion in 1 is the second highest coordination number to date.…”

“…In spite of such a versatile inorganic building block, limited compounds with Preyssler P 5 W 30 as inorganic building block for the construction of modified or extended structures have been reported so far . To our knowledge, the first Preyssler P 5 W 30 -extended network was successfully isolated by Wang et al Following that, Zhang and Yang groups separately reported some Ln-modified P 5 W 30 based inorganic–organic hybrids and related properties. The main difficulties to access them are the following: (i) growth of a single-crystal with high enough quality for X-ray diffraction, and (ii) exploration of suitable pH value for self-assembly.…”

Two New Preyssler‐Type Polyoxometalate‐Based Coordination Polymers and Their Application in Horseradish Peroxidase Immobilization

“…The photoluminescence properties of parent‐ 1 , H 2 biim, 1 , and 2 in the solid state were recorded at room temperature (Figure S11 in the Supporting Information). Parent‐ 1 , 1 , and 2 all display luminescence with three emission bands at λ =433, 450, and 470 nm ( λ ex =280 nm), which could be assigned to ligand to metal charge transfer (LMCT; O→W) . The emission band at λ =345 nm of H 2 biim could be assigned to the π*→π transition.…”

“…W). [42] The emission band at l = 345 nm of H 2 biim could be assigned to the p*!p transition. The emission bands at l = 400 and 415 nm of compounds 1 and 2 mayb ec aused by the coordination of Cu 2 + and H 2 biim, leadingt oL MCT (N!Cu).…”

A New 2D Fluorescent Polyoxometalate Built up of Circular {P5W30} Clusters and Tb3+ Cations

“…[ 24 ] Lately, Yang obtained two organic–inorganic hybrid complexes which have {P 5 W 30 } clusters and TM/Ln‐carboxylate‐Ln linkers, and discussed its luminescent properties. [ 25 ] However, Ln that does not contain organic ligands has rarely been reported so far. The reported POMs based on {P 5 W 30 } cluster can be divided into two main types, one is the metal cation‐encapsulated, the other one is the Preyssler anion was extended into multi‐dimensional structures by coordinated metal‐oxygen bonds.…”