Fluorine Tagging of Polyoxometalates: The Cyclic [{Mo^V₂O₄(H₂O)}₄{O₃PC(CF₃)(O)PO₃}₄]^12–

Abstract

(1), which was structurally characterized in solution by multinuclear NMR spectroscopy and in the solid state by single-crystal X-ray diffraction, infrared, thermogravimetric and elemental analyses. Polyanion 1 crystallizes as the mixed sodium/guanidinium salt Na 6.5 [(H

Syntheses, characterizations and properties of [Mo2O2S2]-based oxothiomolybdenum wheels incorporating bisphosphonate ligands

“…1a). Indeed, as usually observed, 27,32,33 the 1-hydroxyl group of the BP ligand is found to be deprotonated and coordinated to a metal ion in addition to the two oxygen atoms of the phosphonate groups. The eight Mo ions are not coplanar and the wheel is twisted as shown by the side view (Fig.…”

“…Driven by these results, the aim of the present study was to compare the electrocatalytic activity of two analogous compounds, one based on the [Mo 2 O 2 S 2 ] building-unit and the other on the [Mo 2 O 4 ] fragment in order to demonstrate the role of the bridging sulfides in the HER process. To date, a large family of cyclic polyoxomolybdates built from the connections of the [Mo 2 O 4 ] 2+ cations by bisphosphonate ligands (BPs) has been isolated, [27][28][29][30][31][32][33][34] units via hydroxo bridges. Such a spontaneous cyclization process, mainly entropically driven, has allowed the development of relevant host-guest chemistry using various organic ligands as template agents.…”

Polyoxovanadates with Ethylidene-Pyridine Functionalized Bisphosphonate Ligands: Synthesis, Structure, Spectroscopic Characterization, Magnetic, and Antibacterial Studies

“…34 Mialane and co-workers introduced the {Mo V 2 O 4 } unit(s) into bisphosphonate-polyoxometalate assemblies, resulting in a range of compounds with either fully reduced 35−37 or mixedvalent molybdates containing a range of bisphosphonates. 38,39 Derivatives of such polyoxomolybdate-bisphosphonates containing the {Mo V 2 O 4 } unit have also been reported with 2,2,2trifloro-1-hydroxyethane-1,1-bisphosphonate 40 and 1-hydroxy-2-(pyridine-3-yl)ethane-1,1-bisphosphonate. 41 Reports are also present of mixed-metal bisphosphonate-polyoxometalates containing the dimeric {Mo V 2 O 4 } unit with several 3d-block transition metals, such as vanadium(IV), 42 chromium(III), 43 manganese(II), 27 iron(II), 44,45 cobalt(II), and nickel(II), 46,47 containing 1-hydroxyethane-1,1-bisphosphonate, 45,46 4-amino-1-hydroxy-butane-1,1-bisphosphonate, 42 1-hydroxy-4-((pyridin-2-ylmethyl)amino)butane-1,1-bisphosphonate, 43 1-hydroxy-2-(imidazol-1-yl)ethane-1,1-bisphosphonate or its derivatives, 27,44 and 1-hydroxy-2-(pyridine-3-yl)ethane-1,1-bisphosphonate.…”

Organic–inorganic one-dimensional hybrid aggregates constructed from aromatic-bisphosphonate-functionalized polyoxomolybdates

“…5 have been consistently explored for a long time. Subsequently, some other types of hybrids were isolated, for example, the molecular capsule-type derivatives [H 2 V 10 O 18 R 4 ] 8− (R = O 3 PC 6 H 4 PO 3 , O 3 PC 12 H 8 PO 3 ); 6 the C-shaped mixed-valent structure [(Mo V 2 O 4 )(Mo VI 2 O 6 ) 2 {O 3 PC(O)(CH 3 )PO 3 } 2 ] 8− ; 7 the sandwich-type POMs [Ln(H 2 O) 4 (AsW 9 O 33 )(W 2 O 3 )(O 3 PCOHCH 3 PO 3 )Ln(H 2 O) 7 ] 22− (Ln = Ce, Nd, Sm, Eu); 8 the S-shaped polyanions [M{Mo VI 2 O 6 CH 3 C(O)(PO 3 ) 2 } 2 ] n − (M = Co II , Ni II , Cu II , Mn II , Fe III , Cr III ; n = 7, 8), 9 [(Mo 3 O 8 ) 2 (O){O 3 PC(O)(CH 2 -3-C 5 NH 5 )PO 3 } 2 ] 6− ; 10 the cyclohexane-like ring compound [(Mo V 2 O 4 ) 6 (OH) 6 (O 3 PCH 2 PO 3 ) 6 ] 18− ; 11 the windmill-type frameworks [Ln 5 (Mo VI 3 O 8 ){O 3 PC(O)(CH 3 )PO 3 } 6 ] 3− (Ln = Ce III , Pr III , Nd III , Sm III , Eu III , Gd III , Tb III ); 10,12 the cyclic-shape cluster, [{Mo V 2 O 4 (H 2 O)} 4 {O 3 P–C(O)(CF 3 )–PO 3 } 4 ] 12− ; 13 and the aromatic heterocyclic organophosphate-modified complex [(Mo 3 O 8 ){O 3 PC(O)(CH 2 -3-C 5 NH 5 )PO 3 }] 4 8− . 10 These remarkable achievements have confirmed the versatile coordination ability and connection function of bisphosphonate ligands in the structural construction of organic–inorganic POMs, which provided us an excellent opportunity to continuously explore bis-phosphonate-functionalized POMs.…”