Solid state coordination chemistry of the oxofluorovanadium–diphosphonate system in the presence of Cu(II)–tetrapyridylpyrazine complex cations

The Hydrothermal and Structural Chemistry of Oxovanadium−Arylphosphonate Networks and Frameworks

“…An important subclass of these materials is the oxovanadium organophosphonates, − a structurally diverse family of materials characterized by thermal stability of the V−P−O substructure, readily modified organic substituents, and distinct hydrophobic and hydrophilic domains. − A significant characteristic of the oxovanadium organophosphonate materials is the generation of well-defined internal void spaces, , which endow the materials with properties relevant to intercalation, gas storage, or electrooptical applications. − Of particular interest in this regard are the oxovanadium diphosphonate phases, materials constructed of V−P−O layers buttressed by the organic linkers of the {H x O 3 P-tether-PO 3 H y } n − ligand. Despite this recurrent theme, the detailed structural chemistry may be exceedingly complex, reflecting structural determinants such as the tether length of the diphosphonate ligand, the introduction of organic or metal−organic complex cations, and the incorporation of fluoride anions into the inorganic substructure .…”

Metal-organodiphosphonates: Structural consequences of introducing aromatic tethering groups. The structures of [Cu(phen){HO3P(C12H8)PO3H}], [{Cu(phen)}2{HO3P(C12H8)PO3H}] and [Cu(terpy){HO3P(C12H8)PO3H}] and of the bimetallic materials [{Cu(LL)}2MoO2{HO3P(C12H8)PO3H}3] (LL=2,2-bipyridine, o-phenanthroline)

“…Three-dimensional ''pillared layers" and other threedimensional frameworks are the rule for these materials, although the detailed connectivities within the Cu-P-O inorganic layers may exhibit considerable variability. The structural chemistry of copper-organodiphosphonates can be expanded by introducing nitrogen-donor coligands [27][28][29][30][31][32] or by exploiting the copperdiphosphonate moiety in the construction of bimetallic oxide hybrid materials [33][34][35][36][37][38]. Encouraged by the often unique structural chemistry of the parent copper-aromatic-diphosphonates, we have begun to study the chemistry of the Cu/ligand/(aromatic diphosphonate) and Cu/ligand/Mo x O y /(aromatic diphosphonate) systems (where ligand = 2,2-bipyridine (bpy), o-phenanthroline (phen) and 2,2 0 :6;2 00 -terpyridine (terpy)).…”

Hydrothermal synthesis and structure of a two-dimensional bimetallic copper–molybdophosphonate, [{Cu4(H2O)2(phenbisterpy)2(HO3P(CH2)4PO3H)}(Mo4FO12)2{O3P(CH2)4PO3}]·4H2O, constructed from {Mo4FO12}1− clusters and copper-ligand chains (phenbisterpy=1,4-bis(2,2′:6′,2′′-terpyridin-4′-yl)benzene)

“…It is noteworthy that under the hydrothermal conditions of synthesis, HF is commonly introduced as a solubilizing reagent. While the fluoride is intended to be a spectator ion, incorporation to provide metal oxyfluoride species has been observed, generally for the vanadate phases [33][34][35][36][37][38][39][40][41][42][43]. Molybdenum oxyfluoride clusters are much less common, although [ The title compound was prepared from the hydrothermal reaction of Cu(CH 3 CO 2 ) 2 ÁH 2 O, MoO 3 , 1,4-butylenediphosphonic acid, and 1,4-bis(2,2 0 :6 0 ,2 00 -terpyridin-4 0 -yl)benzene in the presence of HF [50].…”