Synthesis and Characterization of Single-Side Organically Grafted Anderson-Type Polyoxometalates

Graphical Five single-side organically decorated Anderson-type molybdoaluminate compounds with R = CH 2 OH, NH 2 , CH 2 CH 3 , NHCH 2 COOH and CH 2 OCH 2 C(CH 2 OH) 3 have been synthesized through one-step and / or controlled reactions. The strategy utilized represents a common approach for the asymmetric modification of Anderson-type molybdoaluminates. Five single-side organic decorated Anderson-type molybdoaluminates have been synthesized from the reaction of the Na 3 (H 2 O) 6 [Al(OH) 6 Mo 6 O 18 ] · 2H 2 O cluster and RC(CH 2 OH) 3 ligands [R = CH 2 OH, NH 2 , CH 2 CH 3 , NHCH 2 COOH, CH 2 OCH 2 C(CH 2 OH) 3 ], followed by the addition of TBA · Br {TBA = [N(C 4 H 9 ) 4 ] + }. The prepared compounds possess an identical Anderson-type structural frame in each case, wherein three of the six hydroxy groups surrounding the Al III heteroatom are substituted by one RC(CH 2 OH) 3 group, forming asymmetric single-sided organically decorated clusters. The compounds demonstrate the simplest synthesis of covalent organic decoration for the single-sides of molybdoaluminates. All the prepared compounds in the present study were synthesized in aqueous solution and characterized by elemental and TG analysis, IR and 1 H NMR spectroscopy, and single-crystal X-ray diffraction analysis. In addition, the supramolecular structures of these compounds based on the hydrogen bonding have also been discussed. The method reported here provides a common approach for the asymmetric functionalization of Anderson-type molybdoaluminates.