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Peter Y Zavalij

Publications and source records attributed to Peter Y Zavalij.

21 records · Page 2Linked to original sources

New structures in the bipyridine-copper(II) nitrate-methanol system: [(bpy)(2)Cu(NO(3))]NO(3) x CH(3)OH and [(bpy)(2)Cu(NO(3))]NO(3).

Reaction of 2,2'-bipyridine (bpy) and copper(II) nitrate in methanol results in two complexes, namely light-blue bis(2,2'-bipyridine)nitratocopper(II) nitrate methanol solvate, [Cu(NO(3))(C(10)H(8)N(2))(2)]NO(3) x CH(3)OH, (I), which is unstable in air, and the product of its decomposition, catena-poly[[[bis(2,2'-bipyridine)copper(II)]-mu-nitrato-O:O'] nitrate], [[Cu(NO(3))(C(10)H(8)N(2))(2)]NO(3)](n), (II). The crystal structures of both compounds were determined from one crystal at room temperature. Later, the structure of (I) was redetermined at low temperature. In (I) and (II), the Cu atom is coordinated by two bpy and one or two nitrate ions, respectively. The second nitrate ion in (I), along with the methanol solvent molecule, is found in the outer coordination sphere, not bonded to Cu. The nitrate in (I) is chelating, while in (II), it bridges (bpy)(2)Cu complexes, forming a one-dimensional chain structure. The Cu cation in (II) lies on a twofold axis and the uncoordinated NO(3)(-) ion is located close to a twofold axis and is therefore disordered. Compound (I) converts into (II) upon loss of solvent.

2,2'-Dipyridyl↗

Ligand influences on copper molybdate networks: the structures and magnetism of [Cu(3,4'-bpy)MoO(4)], [Cu(3,3'-bpy)(0.5)MoO(4)], and [Cu(4,4'-bpy)(0.5)MoO(4)].1.5H(2)O.

The reactions of a Cu(II) salt, MoO(3), and the appropriate bipyridine ligand yield a series of bimetallic oxides, [Cu(3,4'-bpy)MoO(4)] (1), [Cu(3,3'-bpy)(0.5)MoO(4)] (2), and [Cu(4,4'-bpy)(0.5)MoO(4)].1.5H(2)O (3.1.5H(2)O). The structures of 1-3 exhibit three-dimensional covalent frameworks, constructed from bimetallic oxide layers tethered by the dipodal organoimine ligands. However, the [CuMoO(4)] networks are quite distinct. For structure 1, the layer consists of corner-sharing [MoO(4)] tetrehedra and [CuN(2)O(3)] square pyramids, while the layer of 2 is constructed from [MoO(4)] tetrehedra and binuclear [Cu(2)O(6)N(2)] units of edge-sharing copper square pyramids. The oxide substructure of 3 consists of [MoO(4)] tetrahedra corner-sharing with tetranuclear clusters of edge-sharing [CuO(5)N] octahedra. Crystal data: C(10)H(8)N(2)O(4)CuMo (1), orthorhombic Pbca, a = 12.4823(6) A, b = 9.1699(4) A, c = 19.5647(9) A, V = 2239.4(1) A(3), Z = 8; C(5)H(4)NO(4)CuMo (2), triclinic P, a = 5.439(1) A, b = 6.814(1) A, c = 10.727(2) A, alpha = 73.909(4)(o), beta = 78.839(4)(o); gamma = 70.389(4)(o); V = 357.6(1) A(3), Z = 2; C(10)H(8)N(2)O(8)Cu(2)Mo(2).3H(2)O 3.1.5H(2)O, triclinic P, a = 7.4273(7) A, b = 9.2314(8) A, c = 13.880(1) A, alpha = 71.411(2)(o), beta = 88.528(2)(o), gamma = 73.650(2)(o), V = 863.4(1) A(3), Z = 2. The magnetic properties of 1-3 arise solely from the presence of the Cu(II) sites, but reflect the structural differences within the bimetallic oxide layers. Compound 1 exhibits magnetic behavior consistent with ferromagnetic chains which couple antiferromagnetically at low temperature. Compound 2 exhibits strong antiferromagnetic dimeric interactions, with the magnetic susceptibility data consistent with the Bleaney-Bowers equation. Similarly, the magnetic susceptibility of 3 is dominated by antiferromagnetic interactions, which may be modeled as a linear S = 1/2 Heisenberg tetramer.

Journal Article↗

Pb(3)F(5)NO(3), a cationic layered material for anion-exchange.

Our research involves the development of new cationic materials for anion-based applications. We report the solvothermal synthesis and characterization of Pb(3)F(5)NO(3), a new layered lead fluoride material that, unlike the majority of layered and open-framework materials, is cationic in charge. The structure consists of polyhedral lead centers connected by doubly and triply bridging fluoride groups. We quantitatively exchanged the interlamellar nitrate groups of Pb(3)F(5)NO(3) for dichromate, under ambient aqueous conditions. Nuclear magnetic resonance and UV-vis spectroscopy show the reaction proceeds to 61.0% completion in several days. The material is also stable to 450 degrees C, which is vastly superior to organic resins that are still the standard for anion-exchange. The presence of extraframework anions also opens up other potentially unique anion-based properties, such as new catalytic reactions, anion intercalation, or growth of anionic clusters within the void spaces of the cationic material.

Journal Article↗