Syntheses, Crystal Structures And Properties Of Polytungstoarsenate Derivatives Constructed By Organophosphonate Ligands

Polyoxometalates (POMs) have become important inorganic building block due to their intriguing diverse architectures and easy to modify, which is good for the molecular design and assembly. Organophosphonates have a wide varity and applications in medicine, functional materials and catalysis. Thus, the incorporating of organophosphonate into POMs has been widely used due to the potential properties of the obtained compounds. In this paper, we have dedicated ourselves to synthesizing novel organophosphonate-based POWs and obtained several examples according to this strategy. The given compounds were characterized by X-ray single-crystal diffraction, spectroscopy properties, fluorescence, thermogravimetric and alkene epoxidation.1. A series of novel TM-containing ATMP-based POTs, K4H6[H4(AsW9O33)2{M(H2O)W5O11 (N(CH2PO3)3)}2(μ2-O)2]-27H2O[M= Zn (1), Ni (2), Co (3), Mn (4)], have been first prepared in aqueous solution. Polyanions 1-4 can be regarded as two [{(AsW9O33)Zn(H2O)W5O11(N(CH2PO3)3)}(μ2-O)2]9-subunits in opposite directions linked by two μ2-O atoms acting as the "hinge", giving the anion a S-shaped structure. Compound 1 has a good performence in the catelytic oxidation of alkenes.2. Eight members of a new family of ATMP-based POTs rare earth metal complexes, Cs9K7H5{[Ln2(H2O)5W4O6(H2O)2(OH)(AsW9O33)3]2(N(CH2PO3)2)}-23H2O [Ln= PrⅢ (5), DyⅢ (6), HoⅢ (7), ErⅢ (8)] and Cs8K11H{[Ln2(H2O)5W4O6(H2O)3(AsW9O33)3]2(N(CH2PO3)2)}2·22H2O [Ln= SmⅢ (9), Eu Ⅲ (10) GdⅢ (11), TbⅢ (12)], have been synthesized by a one-pot reaction of the precursor [As2W19O67(H2O)]14-, ATMP and lanthanide. The polyoxoanions consist of two flabellum-type 2O)3(AsW9O33)3] units, which are linked by organophosphonate.3. One HEDP-based polyoxotungstate, K10H12[(AsW9O33)2(W8O18)(HO3PCCH3(OH)PO3H)4]·22H2O (13), has been successfully isolated by the conventional aqueous methods, which is comprised of two {AsW9O33} subunits connected by two chains of{W4}.