Effects of reaction gel dehydration on the synthesis of Cu(NC 5H5)4VOF4 and [Cu(NC 5H5)4VOF4][Cu(NC5H 5)4(H2O)VOF4]·H2O

Margaret E. Welk, Charlotte L. Stern, Kenneth R. Poeppelmeier, Alexander J. Norquist

Research output: Contribution to journalArticle

20 Citations (Scopus)

Abstract

The acentric anion, [VOF4]2-, has been incorporated into two new compounds, [Cu(NC5H5)4VOF 4][Cu(NC5H5)4(H2O) VOF4]·H2O and Cu(NC5H5) 4VOF4. Single crystals of both compounds were grown from nearly identical reaction gels under mild hydro(solvo)thermal conditions, which differed only in the inclusion or exclusion of water. While both compounds contain infinite chains, stark differences in structure and composition are observed. The composition of [VOF4]2- dictates the anion's geometry, structure-directing properties, and hydrogen-bonding capacity, and is responsible for the compositional variation between [Cu(NC5H 5)4VOF4][Cu(NC5H5) 4(H2O)VOF4]·H2O and Cu(NC5H5)4VOF4, the observed local and extended order of oxide fluoride anions, and unusual packing motifs. Primary coordination to each [VOF4]2- anion in [(Cu(NC 5H5)4VOF4][Cu(NC5H 5)4(H2O)VOF4]·H2O and Cu(NC5H5)4VOF4 is directed through frans-fluoride ligands, yet variability exists in further sites of interaction. Alignment of V-O bonds in Cu(NC5H5) 4VOF4 results in concerted packing shifts and the destruction of intrachain centers of symmetry. The resulting noncentrosymmetric solid exhibits nonlinear optical activity; the second harmonic generation of Cu(NC5H5)4VOF4 was measured to be 20% of a-quartz using the Kurtz powder technique.

Original languageEnglish
Pages (from-to)956-961
Number of pages6
JournalCrystal Growth and Design
Volume7
Issue number5
DOIs
Publication statusPublished - May 2007

Fingerprint

Dehydration
dehydration
Anions
Negative ions
Gels
gels
anions
synthesis
Fluorides
fluorides
Quartz
optical activity
Harmonic generation
exclusion
Chemical analysis
Powders
Oxides
destruction
harmonic generations
Hydrogen bonds

ASJC Scopus subject areas

  • Chemistry(all)
  • Materials Science(all)
  • Condensed Matter Physics

Cite this

Effects of reaction gel dehydration on the synthesis of Cu(NC 5H5)4VOF4 and [Cu(NC 5H5)4VOF4][Cu(NC5H 5)4(H2O)VOF4]·H2O. / Welk, Margaret E.; Stern, Charlotte L.; Poeppelmeier, Kenneth R.; Norquist, Alexander J.

In: Crystal Growth and Design, Vol. 7, No. 5, 05.2007, p. 956-961.

Research output: Contribution to journalArticle

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title = "Effects of reaction gel dehydration on the synthesis of Cu(NC 5H5)4VOF4 and [Cu(NC 5H5)4VOF4][Cu(NC5H 5)4(H2O)VOF4]·H2O",
abstract = "The acentric anion, [VOF4]2-, has been incorporated into two new compounds, [Cu(NC5H5)4VOF 4][Cu(NC5H5)4(H2O) VOF4]·H2O and Cu(NC5H5) 4VOF4. Single crystals of both compounds were grown from nearly identical reaction gels under mild hydro(solvo)thermal conditions, which differed only in the inclusion or exclusion of water. While both compounds contain infinite chains, stark differences in structure and composition are observed. The composition of [VOF4]2- dictates the anion's geometry, structure-directing properties, and hydrogen-bonding capacity, and is responsible for the compositional variation between [Cu(NC5H 5)4VOF4][Cu(NC5H5) 4(H2O)VOF4]·H2O and Cu(NC5H5)4VOF4, the observed local and extended order of oxide fluoride anions, and unusual packing motifs. Primary coordination to each [VOF4]2- anion in [(Cu(NC 5H5)4VOF4][Cu(NC5H 5)4(H2O)VOF4]·H2O and Cu(NC5H5)4VOF4 is directed through frans-fluoride ligands, yet variability exists in further sites of interaction. Alignment of V-O bonds in Cu(NC5H5) 4VOF4 results in concerted packing shifts and the destruction of intrachain centers of symmetry. The resulting noncentrosymmetric solid exhibits nonlinear optical activity; the second harmonic generation of Cu(NC5H5)4VOF4 was measured to be 20{\%} of a-quartz using the Kurtz powder technique.",
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N2 - The acentric anion, [VOF4]2-, has been incorporated into two new compounds, [Cu(NC5H5)4VOF 4][Cu(NC5H5)4(H2O) VOF4]·H2O and Cu(NC5H5) 4VOF4. Single crystals of both compounds were grown from nearly identical reaction gels under mild hydro(solvo)thermal conditions, which differed only in the inclusion or exclusion of water. While both compounds contain infinite chains, stark differences in structure and composition are observed. The composition of [VOF4]2- dictates the anion's geometry, structure-directing properties, and hydrogen-bonding capacity, and is responsible for the compositional variation between [Cu(NC5H 5)4VOF4][Cu(NC5H5) 4(H2O)VOF4]·H2O and Cu(NC5H5)4VOF4, the observed local and extended order of oxide fluoride anions, and unusual packing motifs. Primary coordination to each [VOF4]2- anion in [(Cu(NC 5H5)4VOF4][Cu(NC5H 5)4(H2O)VOF4]·H2O and Cu(NC5H5)4VOF4 is directed through frans-fluoride ligands, yet variability exists in further sites of interaction. Alignment of V-O bonds in Cu(NC5H5) 4VOF4 results in concerted packing shifts and the destruction of intrachain centers of symmetry. The resulting noncentrosymmetric solid exhibits nonlinear optical activity; the second harmonic generation of Cu(NC5H5)4VOF4 was measured to be 20% of a-quartz using the Kurtz powder technique.

AB - The acentric anion, [VOF4]2-, has been incorporated into two new compounds, [Cu(NC5H5)4VOF 4][Cu(NC5H5)4(H2O) VOF4]·H2O and Cu(NC5H5) 4VOF4. Single crystals of both compounds were grown from nearly identical reaction gels under mild hydro(solvo)thermal conditions, which differed only in the inclusion or exclusion of water. While both compounds contain infinite chains, stark differences in structure and composition are observed. The composition of [VOF4]2- dictates the anion's geometry, structure-directing properties, and hydrogen-bonding capacity, and is responsible for the compositional variation between [Cu(NC5H 5)4VOF4][Cu(NC5H5) 4(H2O)VOF4]·H2O and Cu(NC5H5)4VOF4, the observed local and extended order of oxide fluoride anions, and unusual packing motifs. Primary coordination to each [VOF4]2- anion in [(Cu(NC 5H5)4VOF4][Cu(NC5H 5)4(H2O)VOF4]·H2O and Cu(NC5H5)4VOF4 is directed through frans-fluoride ligands, yet variability exists in further sites of interaction. Alignment of V-O bonds in Cu(NC5H5) 4VOF4 results in concerted packing shifts and the destruction of intrachain centers of symmetry. The resulting noncentrosymmetric solid exhibits nonlinear optical activity; the second harmonic generation of Cu(NC5H5)4VOF4 was measured to be 20% of a-quartz using the Kurtz powder technique.

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