skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Syntheses, structures and characterizations of three novel vanadium selenites with organically bonded copper/nickel complex

Abstract

A series of vanadium selenites covalently bonded with metal-organic complex, namely, Ni(2,2-bipy){sub 2}V{sub 2}O{sub 4}(SeO{sub 3}){sub 2} (1), Cu(2,2-bipy)V{sub 2}O{sub 4}(SeO{sub 3}){sub 2}·0.5H{sub 2}O (2) and Cu{sub 2}(2,2-bipy){sub 2}V{sub 5}O{sub 12}(SeO{sub 3}){sub 2} (3) (2,2-bipy=2,2-bipyridine) have been hydrothermally synthesized and structurally characterized. They exhibit three different structural dimensions, from 0D cluster, 1D chain to 2D layer. Compound 1 features a 0D {Ni(2,2-bipy)_2V_2O_4(SeO_3)_2}{sub 2} dimeric cluster composed of two {Ni(2,2-bipy)_2}{sup 2+} moieties connected by the {V_4O_8(SeO_3)_4}{sup 4-} cluster. Compound 2 shows a 1D {Cu(2,2-bipy)V_2O_4(SeO_3)_2}{sub n} chain in which the {Cu_2(2,2-bipy)_2}{sup 4+} moieties are bridged by the {V_4O_8(SeO_3)_4}{sup 4−} clusters. Compound 3 displays a 2D structure consisted of mixed valence vanadium selenites layers {V"I"VV"V_4Se"I"V_2O_1_8}{sub n}{sup 4−} and {Cu(2,2-bipy)}{sup 2+} complex moieties. The adjacent layers are further interconnected via π-π interactions between the 2,2-bipy ligands exhibiting an interesting 3D supramolecular architecture. Both compound 1 and 2 contain a new {V_4O_8(SeO_3)_4}{sup 4−} cluster and compound 3 exhibits the first 2D vanadate polyhedral layer in vanadium selenites/tellurites with organic moieties. - Graphical abstract: We got three new vanadium selenites with organically linked copper/nickel complex, namely, Ni(2,2-bipy){sub 2}V{sub 2}O{sub 4}(SeO{sub 3}){sub 2} (1), Cu(2,2-bipy)V{sub 2}O{sub 4}(SeO{sub 3}){sub 2}·0.5H{sub 2}O (2) and Cu{sub 2}(2,2-bipy){sub 2}V{sub 5}O{sub 12}(SeO{submore » 3}){sub 2} (3) by hydrothermally syntheses. They display three different structural dimensions, from 0D cluster, to 1D chain and 2D layer. Display Omitted - Highlights: • Three new compounds display three different structural dimensions, from 0D cluster, to 1D chain and 2D layer. • The Tetranuclear {V_4O_8(SeO_3)_4}{sup 4−} cluster and the vanadate {V_5O_1_7}{sub n} 2D layer are observed firstly. • Optical Properties and Magnetic Properties of three compounds are reported.« less

Authors:
 [1];  [2];  [3];  [1];  [2]
  1. College of Chemistry, Fuzhou University, Fuzhou, Fujian 350002 (China)
  2. (China)
  3. State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002 (China)
Publication Date:
OSTI Identifier:
22584097
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 238; Other Information: Copyright (c) 2016 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; BIPYRIDINES; COPPER; HYBRIDIZATION; HYDROTHERMAL SYNTHESIS; INTERACTIONS; LAYERS; LIGANDS; MAGNETIC PROPERTIES; NICKEL; NICKEL COMPLEXES; OPTICAL PROPERTIES; SELENITES; VANADATES; VANADIUM

Citation Formats

Qian, Cheng, State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, Kong, Fang, Mao, Jiang-Gao, E-mail: mjg@fjirsm.ac.cn, and State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002. Syntheses, structures and characterizations of three novel vanadium selenites with organically bonded copper/nickel complex. United States: N. p., 2016. Web. doi:10.1016/J.JSSC.2016.02.044.
Qian, Cheng, State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, Kong, Fang, Mao, Jiang-Gao, E-mail: mjg@fjirsm.ac.cn, & State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002. Syntheses, structures and characterizations of three novel vanadium selenites with organically bonded copper/nickel complex. United States. doi:10.1016/J.JSSC.2016.02.044.
Qian, Cheng, State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, Kong, Fang, Mao, Jiang-Gao, E-mail: mjg@fjirsm.ac.cn, and State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002. 2016. "Syntheses, structures and characterizations of three novel vanadium selenites with organically bonded copper/nickel complex". United States. doi:10.1016/J.JSSC.2016.02.044.
@article{osti_22584097,
title = {Syntheses, structures and characterizations of three novel vanadium selenites with organically bonded copper/nickel complex},
author = {Qian, Cheng and State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002 and Kong, Fang and Mao, Jiang-Gao, E-mail: mjg@fjirsm.ac.cn and State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002},
abstractNote = {A series of vanadium selenites covalently bonded with metal-organic complex, namely, Ni(2,2-bipy){sub 2}V{sub 2}O{sub 4}(SeO{sub 3}){sub 2} (1), Cu(2,2-bipy)V{sub 2}O{sub 4}(SeO{sub 3}){sub 2}·0.5H{sub 2}O (2) and Cu{sub 2}(2,2-bipy){sub 2}V{sub 5}O{sub 12}(SeO{sub 3}){sub 2} (3) (2,2-bipy=2,2-bipyridine) have been hydrothermally synthesized and structurally characterized. They exhibit three different structural dimensions, from 0D cluster, 1D chain to 2D layer. Compound 1 features a 0D {Ni(2,2-bipy)_2V_2O_4(SeO_3)_2}{sub 2} dimeric cluster composed of two {Ni(2,2-bipy)_2}{sup 2+} moieties connected by the {V_4O_8(SeO_3)_4}{sup 4-} cluster. Compound 2 shows a 1D {Cu(2,2-bipy)V_2O_4(SeO_3)_2}{sub n} chain in which the {Cu_2(2,2-bipy)_2}{sup 4+} moieties are bridged by the {V_4O_8(SeO_3)_4}{sup 4−} clusters. Compound 3 displays a 2D structure consisted of mixed valence vanadium selenites layers {V"I"VV"V_4Se"I"V_2O_1_8}{sub n}{sup 4−} and {Cu(2,2-bipy)}{sup 2+} complex moieties. The adjacent layers are further interconnected via π-π interactions between the 2,2-bipy ligands exhibiting an interesting 3D supramolecular architecture. Both compound 1 and 2 contain a new {V_4O_8(SeO_3)_4}{sup 4−} cluster and compound 3 exhibits the first 2D vanadate polyhedral layer in vanadium selenites/tellurites with organic moieties. - Graphical abstract: We got three new vanadium selenites with organically linked copper/nickel complex, namely, Ni(2,2-bipy){sub 2}V{sub 2}O{sub 4}(SeO{sub 3}){sub 2} (1), Cu(2,2-bipy)V{sub 2}O{sub 4}(SeO{sub 3}){sub 2}·0.5H{sub 2}O (2) and Cu{sub 2}(2,2-bipy){sub 2}V{sub 5}O{sub 12}(SeO{sub 3}){sub 2} (3) by hydrothermally syntheses. They display three different structural dimensions, from 0D cluster, to 1D chain and 2D layer. Display Omitted - Highlights: • Three new compounds display three different structural dimensions, from 0D cluster, to 1D chain and 2D layer. • The Tetranuclear {V_4O_8(SeO_3)_4}{sup 4−} cluster and the vanadate {V_5O_1_7}{sub n} 2D layer are observed firstly. • Optical Properties and Magnetic Properties of three compounds are reported.},
doi = {10.1016/J.JSSC.2016.02.044},
journal = {Journal of Solid State Chemistry},
number = ,
volume = 238,
place = {United States},
year = 2016,
month = 6
}
  • Three new organically bonded indium(III) selenates or selenites, namely, In{sub 2}(2,2'-bipy){sub 2}(SeO{sub 4}){sub 3}(H{sub 2}O){sub 2}.2H{sub 2}O (1), In{sub 2}(2,2'-bipy){sub 2}(SeO{sub 4})(C{sub 2}O{sub 4}){sub 2}.0.5H{sub 2}O (2) and In{sub 2}(2,2'-bipy){sub 2}(SeO{sub 3}){sub 2}(C{sub 2}O{sub 4}) (3) (2,2'-bipy=2,2'-bipyridine) have been synthesized by hydro/solvothermal reactions by using the in situ ligand synthesis technique (2 and 3) and structurally characterized. The structure of compound 1 features a dimer composed of two InO{sub 4}N{sub 2} octahedra bridged by three SeO{sub 4} tetrahedra via cornering sharing. The structure of compound 2 shows a 2D inorganic-organic hybrid layer in which the indium (III) ions are bridgedmore » by both selenate and oxalate anions, whereas the structure of compound 3 possesses a 2D inorganic-organic hybrid layer composed of the indium (III) ions interconnected by both selenite and oxalate anions. The adjacent layers are further interconnected via {pi}...{pi} interactions between the bipy ligands. Compound 1 displays an intra-ligand luminescent emission band at {lambda}{sub max}=360 nm whereas compounds 2 and 3 both exhibit intra-ligand luminescent emission bands at {lambda}{sub max}=389 nm. - Graphical abstract: Three new organically bonded indium(III) selenates or selenites hybrids have been synthesized and characterized. Their structures feature organically bonded indium oxalate selenate or selenite layer or hydrogen-bonded 3D structures based on indium selenate dimers.« less
  • Al{sub 2}(SeO{sub 3}){sub 3} {center dot} 6H{sub 2}O and AlH(SeO{sub 3}){sub 2} {center dot} 2H{sub 2}O were prepared hydrothermally at 70C. Al{sub 2}(SeO{sub 3}){sub 3} {center dot} 6H{sub 2}O is trigonal (space group P31 c) with a = 8.8020(6) and c = 10.7070(8) {angstrom}, Z = 2, V = 718.39 {angstrom}{sup 3}, 1,377 observed reflections (I > 3{sigma}(I)), R = 3.27%, and R{sub w} = 3.55%. The structure consists of discrete Al{sub 2}(SeO{sub 3}){sub 3} {center dot} 6H{sub 2}O units which are linked via hydrogen bonding to form an open structure with channels running parallel to the (0001) direction. AlH(SeO{submore » 3}){sub 2} {center dot} 2H{sub 2}O is monoclinic (P2{sub 1}/n) with a = 7.3853(5), b = 6.4895(6), and c = 7.3958(7) {angstrom}, {beta} = 106.28(9){degree}, Z = 2, V = 340.24 {angstrom}{sup 3}, 732 observed reflections, R = 4.04%, and R{sub w} = 3.98%. The structure consists of octahedral AlO{sub 6} units which are interlinked via the sharing of vertices with four separate selenite groups. The selenite groups form dimers which appear to contain a symmetry-restricted hydrogen bond. This symmetry-restricted bond is markedly shorter than the other hydrogen bonds in the structure. The infrared spectra and thermal decomposition behavior of both compounds are also reported.« less
  • Three new hydrated scandium selenites have been hydrothermally synthesized as single crystals and structurally and physically characterized. Sc2(SeO3)3.H2O crystallizes as a new structure type containing novel ScO7 pentagonal bipyramidal and ScO6+1 capped octahedral coordination polyhedra. Sc2(SeO3)3.3H2O contains typical ScO6 octahedra and is isostructural with its M2(SeO3)3.3H2O (M=Al, Cr, Fe, Ga) congeners. CsSc3(SeO3)4(HSeO3)2.2H2O contains near-regular ScO6 octahedra and has essentially the same structure as its indium-containing analogue. All three phases contain the expected pyramidal [SeO3]2- selenite groups. Crystal data: Sc2(SeO3)3.3H2O, Mr=524.85, trigonal, R3c (No. 161), a=9.6481(5)A, c=20.7832(12)A, V=1675.45(16)A3, Z=6, R(F)=0.018, wR(F2)=0.036; Sc2(SeO3)3.H2O, Mr=488.82, orthorhombic, P212121 (No. 19), a=6.5913(6)A, b=11.1596(11)A, c=12.1368(11)A, V=892.74(14)A3,more » Z=4, R(F)=0.051, wR(F2)=0.086; CsSc3(SeO3)4(HSeO3)2.2H2O, Mr=1067.60, orthorhombic, Pnma (No. 62), a=16.670(3)A, b=13.167(3)A, c=9.575(2)A, V=2101.6(7)A3, Z=4, R(F)=0.035, wR(F2)=0.070.« less
  • Three new sodium cobalt (nickel) selenite compounds, namely, Na{sub 2}Co{sub 2}(SeO{sub 3}){sub 3}, Na{sub 2}Co{sub 1.67}Ni{sub 0.33}(SeO{sub 3}){sub 3}, and Na{sub 2}Ni{sub 2}(SeO{sub 3}){sub 3} have been hydro-/solvothermally synthesized in the mixed solvents of acetonitrile and water. Single-crystal X-ray diffraction analyses reveal that these isostructural compounds belong to the orthorhombic Cmcm space group and their structures feature three-dimensional open frameworks constructed by the two-dimensional layers of [MSeO{sub 3}] pillared by the [SeO{sub 3}]{sup 2-} groups. The two different types of Na{sup +} ions reside in the intersecting two-dimensional channels parallel to the a- and c-axes, respectively. Their thermal properties havemore » been investigated via TGA-DSC. The magnetic measurements indicate the existence of the antiferromagnetic interactions in these compounds. - Graphical abstract: Three new isostructural metal selenites, Na{sub 2}Co{sub 2}(SeO{sub 3}){sub 3}, Na{sub 2}Co{sub 1.67}Ni{sub 0.33}(SeO{sub 3}){sub 3}, and Na{sub 2}Ni{sub 2}(SeO{sub 3}){sub 3} have been hydro-/solvothermally synthesized and characterized. Their structures feature three-dimensional open frameworks with Na{sup +}-occupied channels.« less
  • Systematic explorations in vanadium arsenites and arsenates led to the isolation four new compounds, namely, {alpha}-(V{sup IV}O){sub 3}(As{sup III}O{sub 3}){sub 2} (1), {beta}-(V{sup IV}O){sub 3}(As{sup III}O{sub 3}){sub 2} (2), (V{sup IV}O)[V{sup IV}O(H{sub 2}O)]{sub 2}(As{sup V}O{sub 4}){sub 2} (3), V{sup III}V{sup IV}O{sub 2}(As{sup V}O{sub 4}) (4). Compounds 1, 2 and 4 were synthesized by standard solid-state reactions, and compound 3 is a vanadium arsenate dihydrate synthesized through hydrothermal reactions. Compounds 1 and 2 are isomers, and they represent the first examples of ternary inorganic vanadium(IV) arsenites. Single crystal X-ray diffraction analysis indicated that the four compounds display four different structural types.more » Magnetic property measurements for compound 1 indicated that it exhibits ferromagnetism with the Curie temperature T{sub c}=65 K. Thermal stability and optical properties for compounds 1 and 3 were also investigated. - Graphical abstract: Hydrothermal or solid state reactions of V{sub 2}O{sub 5} (or VO{sub 2}) and As{sub 2}O{sub 3} yielded four new ternary compounds with four different types of structures, namely, {alpha}-(VO){sub 3}(AsO{sub 3}){sub 2} (1), {beta}-(VO){sub 3}(AsO{sub 3}){sub 2} (2), (VO)[VO(H{sub 2}O)]{sub 2}(AsO{sub 4}){sub 2} (3), (VO){sub 2}(AsO{sub 4}) (4). {alpha}-(VO){sub 3}(AsO{sub 3}){sub 2} (1), {beta}-(VO){sub 3}(AsO{sub 3}){sub 2} (2) represent the first examples of ternary inorganic vanadium(IV) arsenites. Highlights: Black-Right-Pointing-Pointer Hydrothermal or solid state reactions of V{sub 2}O{sub 5} (or VO{sub 2}) and As{sub 2}O{sub 3} yielded two new arsenites. Black-Right-Pointing-Pointer They represent the first examples of ternary vanadium arsenites. Black-Right-Pointing-Pointer Two new ternary vanadium arsenates were also obtained. Black-Right-Pointing-Pointer They exhibit four different structural types.« less