Synthesis, Structure, and Photochemistry of an Organic Heptamolybdate‐Monomolybdate

Abstract

Treatment of MoO3 with butan‐1‐amine (BuNH2) or pyrrolidine (PyrNH2) results in the formation of (BuNH3)8[(Mo7O24)(MoO4)]·3H2O (1; BuNH3 = butan‐1‐aminium) or (PyrNH2)6[(Mo7O24]·2H2O (2; PyrNH2 = pyrrolidinium), respectively. On irradiation with sunlight, compound 1, which is an organic heptamolybdate [Mo7O24]6– that contains a cocrystallized monomolybdate [MoO4]2– in the same compound, is transformed to an oxido‐bridged diheptamolybdate (BuNH3)10[(Mo7O22)(μ2‐O)2(Mo7O22)]·5.5H2O (1b). The [Mo7O24]6– units in 1 and 2 are made up of edge‐sharing [MoO6] octahedra, whereas the central unit in 1b is a bis(μ2‐O)‐bridged heptamolybdate dimer. Hydrogen bonding among the lattice water molecules in 1 results in the formation of a water octamer, whereas hydrogen bonding between the lattice water molecules and [Mo7O24]6– in 2 results in the formation of a one‐dimensional water‐linked heptamolybdate chain. Supramolecular structures, photochemistry, and thermal properties of 1, 1b, and 2 are reported. For comparison of photochemical behavior, two more polyoxomolybdates, (PrNH3)6[Mo7O24]·3H2O (3; PrNH3 = propan‐1‐aminium) and (PentNH3)6[Mo7O24]·3H2O (4; PentNH3 = pentan‐1‐aminium), were prepared and characterized.

In situ ligand exchange-mediated 0D/1D transformation of a polyoxovanadate

“…† All values are typical for strong hydrogen bonds reported for water clusters. [30][31][32][33][34] Following the nomenclature suggested by Infantes et al [35][36][37] the cluster can be defined as U0 type for cross-linked discrete rings, namely U02 2)2(2)5(2)5(2)5(3)5(3 In many structures of POVs water molecules are observed, which are frequently disordered preventing the identification of water clusters. Hence, the occurrence of the (H 2 O) 16 cluster is unusual in Sb-POV chemistry.…”

Synthesis, characterization and photochemistry of a new heptamolybdate supported magnesium-aqua coordination complex

“…21 The final product of the acidification is MoO 3 , while the first product (∼pH6), is the heptamolybdate [Mo 7 O 24 ] 6− anion 22 which has been isolated with a variety of counter cations. 23 The ability of [Mo 7 O 24 ] −6 to function as a pure "inorganic ligand" has made it possible to use it as a building block 24 for the synthesis of new materials. A literature survey (table 1) reveals the rich coordination chemistry of the heptamolybdate ligand.…”

The Anderson–Evans polyoxometalate: From inorganic building blocks via hybrid organic–inorganic structures to tomorrows “Bio-POM”

“…Mo 6 [93,175,[218][219][220], Co II/III Mo6 [221][222][223] FeIII Mo 6 [224], Cu II Mo6 [174,[225][226][227][228][229], Zn II Mo6 [230], AsIII Mo 6 [229][230][231][232],Mo 7 [112,176,193,[233][234][235][236][237][238][239][240][241][242][243][244][245], Te VI Mo6 [70,[246][247][248][249][250], Te VI W 6[70,75,[251][252]…”