TY - JOUR
T1 - Polyoxometalates functionalized by bisphosphonate ligands
T2 - Synthesis, structural, magnetic, and spectroscopic characterizations and activity on tumor cell lines
AU - El Moll, Hani
AU - Zhu, Wei
AU - Oldfield, Eric
AU - Rodriguez-Albelo, L. Marleny
AU - Mialane, Pierre
AU - Marrot, Jérôme
AU - Vila, Neus
AU - Mbomekallé, Israel Martyr
AU - Rivière, Eric
AU - Duboc, Carole
AU - Dolbecq, Anne
PY - 2012/7/16
Y1 - 2012/7/16
N2 - Figure Persented: We report the synthesis and characterization of eight new Mo, W, or V-containing polyoxometalate (POM) bisphosphonate complexes with metal nuclearities ranging from 1 to 6. The compounds were synthesized in water by treating MoVI, WVI, VIV, or VV precursors with biologically active bisphosphonates H2O 3PC(R)(OH)PO3H2 (R = C3H 6NH2, Ale; R = CH2S(CH3) 2, Sul and R = C4H5N2, Zol, where Ale = alendronate, Sul = (2-Hydroxy-2,2-bis-phosphono-ethyl)-dimethyl-sulfonium and Zol = zoledronate). Mo6(Sul)2 and Mo 6(Zol)2 contain two trinuclear MoVI cores which can rotate around a central oxo group while Mo(Ale)2 and W(Ale) 2 are mononuclear species. In V5(Ale)2 and V5(Zol)2 a central VIV ion is surrounded by two VV dimers bound to bisphosphonate ligands. V6(Ale) 4 can be viewed as the condensation of one V5(Ale) 2 with one additional VIV ion and two Ale ligands, while V3(Zol)3 is a triangular VIV POM. These new POM bisphosphonates complexes were all characterized by single-crystal X-ray diffraction. The stability of the Mo and W POMs was studied by 31P NMR spectroscopy and showed that all compounds except the mononuclear Mo(Ale)2 and W(Ale)2 were stable in solution. EPR measurements performed on the vanadium derivatives confirmed the oxidation state of the V ions and evidenced their stability in aqueous solution. Electrochemical studies on V5(Ale)2 and V 5(Zol)2 showed reduction of VV to V IV, and magnetic susceptibility investigations on V 3(Zol)3 enabled a detailed analysis of the magnetic interactions. The presence of zoledronate or vanadium correlated with the most potent activity (IC50-1-5 μM) against three human tumor cell lines.
AB - Figure Persented: We report the synthesis and characterization of eight new Mo, W, or V-containing polyoxometalate (POM) bisphosphonate complexes with metal nuclearities ranging from 1 to 6. The compounds were synthesized in water by treating MoVI, WVI, VIV, or VV precursors with biologically active bisphosphonates H2O 3PC(R)(OH)PO3H2 (R = C3H 6NH2, Ale; R = CH2S(CH3) 2, Sul and R = C4H5N2, Zol, where Ale = alendronate, Sul = (2-Hydroxy-2,2-bis-phosphono-ethyl)-dimethyl-sulfonium and Zol = zoledronate). Mo6(Sul)2 and Mo 6(Zol)2 contain two trinuclear MoVI cores which can rotate around a central oxo group while Mo(Ale)2 and W(Ale) 2 are mononuclear species. In V5(Ale)2 and V5(Zol)2 a central VIV ion is surrounded by two VV dimers bound to bisphosphonate ligands. V6(Ale) 4 can be viewed as the condensation of one V5(Ale) 2 with one additional VIV ion and two Ale ligands, while V3(Zol)3 is a triangular VIV POM. These new POM bisphosphonates complexes were all characterized by single-crystal X-ray diffraction. The stability of the Mo and W POMs was studied by 31P NMR spectroscopy and showed that all compounds except the mononuclear Mo(Ale)2 and W(Ale)2 were stable in solution. EPR measurements performed on the vanadium derivatives confirmed the oxidation state of the V ions and evidenced their stability in aqueous solution. Electrochemical studies on V5(Ale)2 and V 5(Zol)2 showed reduction of VV to V IV, and magnetic susceptibility investigations on V 3(Zol)3 enabled a detailed analysis of the magnetic interactions. The presence of zoledronate or vanadium correlated with the most potent activity (IC50-1-5 μM) against three human tumor cell lines.
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U2 - 10.1021/ic3010079
DO - 10.1021/ic3010079
M3 - Article
C2 - 22725619
AN - SCOPUS:84863928443
SN - 0020-1669
VL - 51
SP - 7921
EP - 7931
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 14
ER -