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ORGANOFUNCTIONALIZED OXOMETALATES: SYNTHESIS, STRUCTURE, AND PROPERTIES OF A NEW CLASS OF MIXED-METAL TETRAMETALATE CLUSTERS
Title
ORGANOFUNCTIONALIZED OXOMETALATES: SYNTHESIS, STRUCTURE, AND PROPERTIES OF A NEW CLASS OF MIXED-METAL TETRAMETALATE CLUSTERS
Creator
Shuaib, Damola Taye
Date
2022
Description
Oxometalates (OMs) are metal-oxide clusters with addenda mental atom mainly V, Mo, and W and bridged by oxide anions. Prototypical examples...
Show moreOxometalates (OMs) are metal-oxide clusters with addenda mental atom mainly V, Mo, and W and bridged by oxide anions. Prototypical examples like polyoxometalates (POMs) are completely inorganic. While clusters with nuclearities ranging from 6 to 18 are common for purely inorganic examples, those with less than nuclearity 6 are rare. Therefore, functionalization by covalent interaction with organic moiety via self-assembly has been utilized as a viable route for making compact clusters with nuclearity of 4 and below. These compounds constitute the organo-functionalized examples of the purely inorganic structure ([XMaOb]n-) POM. Reports of organo-functionalized tetrametalates (TMs), ([MxOyLz])n- (where M = metal, x = 4 and L represents an organic ligand) are sparse. Mixed metal species are especially interesting as potential redox active materials as they contain energetically distinct potential redox centers. OMs have ability to accept electrons in a chemically reversible manner through the terminal oxo-ligand (M=Ot) leading to dπ–pπ electron transfer. Considering the rich structural and electronic properties of these complexes, four neutral mixed-metal (M-V) tetrametalate clusters, [(CoIICl)2(VIVO)2{((HOCH2CH2)(H)N(CH2CH2O))(HN(CH2CH2O)2}2] (1), [(ZnIICl)2(VIVO)2{((HOCH2CH2)(H)N(CH2CH2O))(HN(CH2CH2O)2}2] (2), [CoII2(VIVOF)2{((HOCH2CH2)(H)N(CH2CH2O))(HN(CH2CH2O)2)}2] (3), and [ZnII2(VIVOF)2{((HOCH2CH2)(H)N(CH2CH2O))(HN(CH2CH2O)2)}2] (4) containing unprecedented oxometallocyclic {M2V2X2N4O8}(M = Co, Zn; X = F, Cl) frameworks decorated with diethanolamine ligand in bidentate and tridentate manners. The type of halo-ligand has direct influence on the geometry of the metal M and UV-Vis reflectance spectra revealed changes in electronic structure consistent with charge transfer processes expected. Computational and magnetic properties studies revealed that the ground state multiplicity of 1 is confirmed as an open-shell singlet with a prediction of an isotropic exchange coupling of -6.6 cm-1 but less clear for 2. The vanadium centers are best described as a V(IV) center and the cobalt centers are high-spin Co(II) centers. Less orbital destabilization was observed due to weaker interaction of Cl- ligand on Co than what was observed for O2- ligand on V centers. In 2, there are four weakly coupled spin centers, where the isotropic exchange couplings are defined as J1, J2’, and J2’’. These couplings are approximated as J1 = 1.5/+11.7 cm-1, J2’ = -22.1/-14.8 cm-1, and J2’’ = +4.2/+4.8 cm-1. Although J2’’ is predicted to be weakly ferromagnetic in nature, whereas the fit suggested a weak antiferromagnetic interaction for each of the V(IV)-Co(II) couplings. The low-temperature magnetic susceptibility suggests a Type III spin frustration present in the system. However, competing magnetic interactions are known to be operative in tetranuclear system which is even observed to be more prominent in the mixed-metal tetranuclear system considering the edge-sharing consequence on magnetic behavior. A new route to metal complex synthesis via in situ ligand transformation from diethanolamine to bicine by disproportionation and oxidation reactions yielded three isostructural mononuclear clusters Bis[N,N-bis(2-hydroxyethyl)glycinato]-Cobalt(II) 5, Bis[N,N-bis(2-hydroxyethyl)glycinato]-Nickel(II) 6, and Bis[N,N-bis(2-hydroxyethyl)glycinato]-Copper(II) 7. The observed transformation is predicted to proceed through nucleophilic substitution (SN2) as expected for substituted ammines. These metal complexes are characterized by various analytical techniques such as, FT-IR and UV-Vis spectroscopies, single crystal and powdered X-ray diffraction analyses, Energy-Dispersed X-ray spectroscopy, magnetic properties measurements, thermal gravimetric analysis, bond valence sum calculations etc. Based on their features and detailed structure-property-application analyses, the clusters showed great potentials for catalysis, materials for digital tools, chemical sensing, molecular magnets and precursors as molecular building blocks for extended open frameworks.
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