A new octamolybdate: Observation of the θ-isomer in [Fe(tpyprz) 2]2[Mo8O26]·3.7H 2O (tpyprz=tetra-2-pyridylpyrazine)

Damian G. Allis; Eric Burkholder; Jon Zubieta

doi:10.1016/j.poly.2004.01.011

A new octamolybdate: Observation of the θ-isomer in [Fe(tpyprz) ₂]₂[Mo₈O₂₆]·3.7H ₂O (tpyprz=tetra-2-pyridylpyrazine)

Damian G. Allis, Eric Burkholder, Jon Zubieta

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

107 Scopus citations

Abstract

The hydrothermal reaction of Fe(CH₃CO₂)₂, tetra-2-pyridylpyrazine (tpyprz) and (NH₄)₆Mo ₇O₂₄·4H₂O yields purple crystals of [Fe(tpyprz)₂]₂[Mo₈O₂₆]·3. 7H₂O. The discrete octamolybdate anions represent a new isomeric form, θ-[Mo₈O₂₆]^4-. The cluster anion consists of four octahedra, two square pyramids, and two tetrahedra in an edge- and corner-sharing arrangement. A computational study of the isomer using both a single-point energy calculation of the crystallographic coordinates and a geometry optimization of the isomer at the Restricted Hartree-Fock level of theory illustrates the similarities of the θ-isomer and the low energy δ-isomer reported previously.

Original language	English (US)
Pages (from-to)	1145-1152
Number of pages	8
Journal	Polyhedron
Volume	23
Issue number	7
DOIs	https://doi.org/10.1016/j.poly.2004.01.011
State	Published - Apr 15 2004

Keywords

Building block approach
Hartree-Fock calculations
Hydrothermal synthesis
Octamolybdate
Organic-inorganic hybrid
Three-dimensional oxide

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

Access to Document

10.1016/j.poly.2004.01.011

Cite this

@article{c0e99f7c50784d70b46fb6b19b49775e,

title = "A new octamolybdate: Observation of the θ-isomer in [Fe(tpyprz) 2]2[Mo8O26]·3.7H 2O (tpyprz=tetra-2-pyridylpyrazine)",

abstract = "The hydrothermal reaction of Fe(CH3CO2)2, tetra-2-pyridylpyrazine (tpyprz) and (NH4)6Mo 7O24·4H2O yields purple crystals of [Fe(tpyprz)2]2[Mo8O26]·3. 7H2O. The discrete octamolybdate anions represent a new isomeric form, θ-[Mo8O26]4-. The cluster anion consists of four octahedra, two square pyramids, and two tetrahedra in an edge- and corner-sharing arrangement. A computational study of the isomer using both a single-point energy calculation of the crystallographic coordinates and a geometry optimization of the isomer at the Restricted Hartree-Fock level of theory illustrates the similarities of the θ-isomer and the low energy δ-isomer reported previously.",

keywords = "Building block approach, Hartree-Fock calculations, Hydrothermal synthesis, Octamolybdate, Organic-inorganic hybrid, Three-dimensional oxide",

author = "Allis, {Damian G.} and Eric Burkholder and Jon Zubieta",

note = "Funding Information: This work was supported by a grant from the National Science Foundation, CHE-0242153.",

year = "2004",

month = apr,

day = "15",

doi = "10.1016/j.poly.2004.01.011",

language = "English (US)",

volume = "23",

pages = "1145--1152",

journal = "Polyhedron",

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publisher = "Elsevier",

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T2 - Observation of the θ-isomer in [Fe(tpyprz) 2]2[Mo8O26]·3.7H 2O (tpyprz=tetra-2-pyridylpyrazine)

AU - Allis, Damian G.

AU - Burkholder, Eric

AU - Zubieta, Jon

N1 - Funding Information: This work was supported by a grant from the National Science Foundation, CHE-0242153.

PY - 2004/4/15

Y1 - 2004/4/15

N2 - The hydrothermal reaction of Fe(CH3CO2)2, tetra-2-pyridylpyrazine (tpyprz) and (NH4)6Mo 7O24·4H2O yields purple crystals of [Fe(tpyprz)2]2[Mo8O26]·3. 7H2O. The discrete octamolybdate anions represent a new isomeric form, θ-[Mo8O26]4-. The cluster anion consists of four octahedra, two square pyramids, and two tetrahedra in an edge- and corner-sharing arrangement. A computational study of the isomer using both a single-point energy calculation of the crystallographic coordinates and a geometry optimization of the isomer at the Restricted Hartree-Fock level of theory illustrates the similarities of the θ-isomer and the low energy δ-isomer reported previously.

AB - The hydrothermal reaction of Fe(CH3CO2)2, tetra-2-pyridylpyrazine (tpyprz) and (NH4)6Mo 7O24·4H2O yields purple crystals of [Fe(tpyprz)2]2[Mo8O26]·3. 7H2O. The discrete octamolybdate anions represent a new isomeric form, θ-[Mo8O26]4-. The cluster anion consists of four octahedra, two square pyramids, and two tetrahedra in an edge- and corner-sharing arrangement. A computational study of the isomer using both a single-point energy calculation of the crystallographic coordinates and a geometry optimization of the isomer at the Restricted Hartree-Fock level of theory illustrates the similarities of the θ-isomer and the low energy δ-isomer reported previously.

KW - Building block approach

KW - Hartree-Fock calculations

KW - Hydrothermal synthesis

KW - Octamolybdate

KW - Organic-inorganic hybrid

KW - Three-dimensional oxide

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