Syntheses,Structures And Properties Of Transition-Metal-Substituted Polyoxomolybdates Constructed By Organophosphonates

Organophosphonates are a unique class of organic ligands with the potential applications in medicine, materials and catalysis. Polyoxometalates?POMs?, with intriguing structures and excellent properties, have become important inorganic building blocks due to the strong coordination ability of the surface oxygen atoms on POMs. Recently, the field of organophosphonate-functionalized polyoxomolybdates?PODs? has been extensively explored. In this Master Degree Thesis, three series of transition-metal?TM?-substituted organophosphonate-functionalized PODs have been successfully synthesized based on the molecular design and assembly. The presented compounds were further characterized by single crystal X-ray diffraction, X-ray powder diffraction, elemental analyses, thermogravimetric analyses, X-ray photoelectron spectroscopy, IR and UV-vis spectra, magnetic properties and the activity in degradation organic dyes.This dissertation contains:By introducing glyphosate and transition metals into the PODs system, three members of a new family of TM-substituted glyphosate-functionalized PODs have been synthesized in aqueous solution.CsNa₉[H₂{Ni₃O₂?H₂O?₆}?PMo₆O₂1?2{Ni?OOCCH₂NHCH₂PO₃?₂}3]·21H₂O?1? Cs₂Na₈[H₆{Co?H₂O?₄}₃?SeMo₆O₂1?2{Co?OOCCH₂NCH₂PO₃?2}3]·15H₂O?2? Cs₂Na₉H₃[H₆{Ni?H₂O?₄}?Se Mo6O₂1?2{Ni?OOCCH₂NCH₂PO₃?2}3]·18H₂O?3?Six novel TM-substituted risedronate-functionalized PODs have been presented through conventional aqueous solution by a one-pot reaction of the precursor Na₂HPMo₁2O₄0·14H₂O, TM and Risedronic acid.Cs₄Na₂[{Ni O?H₂O?2}?Mo₂O₅L?]₂·14H₂O?4? Cs₄Na₂[{Co O?H₂O?₂}?Mo₂O₅L?]2·14H₂O?5? Cs2Na2H[?Cr O₂?{?Mo₂O₅??HL?}₂]·15H₂O?6? Cs₁0Na₄H₈[Mn O₂{HL?Mo₂O₅?Mn O₂?H₂O??Mo₂O₄?L}₂]2·26H₂O?7? Na6H[?Mn O₂?{?Mo₂O₅?L}2]·16H₂O?8? Cs₅Na₂[?Cr O₂?{?Mo₂O₅?L}2]·15H₂O?9?Two members of a new family of TM-containing HEDP-functionalized PODs and one HEDP-functionalized PODs have been successfully obtained in aqueous or mixed solution by the mixing of the Keggin-type precursor Na₂HPMo₁2O₄0·14H₂O, HEDP and the additional TM chloride.Na₇H[Ni O₂{Mo₂O₅?O₃PCH₃C?O?PO₃?}2]·28H₂O?10? Na₈[Co O₂{Mo₂O₅?O₃PCH₃C?O?PO₃?}2]·24H₂O?11? Na5[?Mo2O6??O₃PCH3C?O?PO₃?]·14H₂O?12?...