Synthesis and properties of N3 and CN delivery compounds and related precursors for nitride and ceramic fabrication

Jesse B. Tice, C. J. Ritter, Andrew Chizmeshya, Brandon Forrest, Levi Torrison, T. L. Groy, John Kouvetakis

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

The simple azido and cyano compounds Cl2AsN3, Br 2AsN3, (C6H5)SiH2N 3, (C6H5)SiH2CN and p-(tolyl)SiH2CN have been prepared for the first time by metathesis reactions involving the corresponding halides and NaN3, LiN 3 and LiCN. These compounds represent a highly reactive and efficient family of delivery reagents for the preparation of N3 and CN molecular precursors to bulk ceramics and nitride thin films. They are isolated as low volatility liquids and characterized by spectroscopic methods and chemical analysis. Ab initio simulations were used to elucidate the structural and vibrational properties of the simpler, fully inorganic Cl 2AsN3 and Br2AsN2 species. This theoretical treatment was extended to include the hypothetical H 2AsN3 and HClAsN3 derivatives which are particularly desirable as single-source low-temperature As-N sources for the formation of highly sought after, metastable GaAs1-xNx materials for solar cell applications. The practical utility of the title molecules is also demonstrated by synthesizing several representative compounds of B, Be, Ga and Al, which are of interest for the development of open frameworks, optoelectronic nitrides and refractory B-C-N hybrids. The cyanide derivatives (C6H5)SiH2CN and p-(tolyl)SiH 2CN react readily with Be and B halides to yield crystalline Be(CN)2 and amorphous B-C-N. The latter is crystallized upon heating to form graphite-like polymorphs with homogeneous nanoscale morphologies. The azide derivatives Cl2AsN3, Br2AsN3 and (C6H5)SiH2N3 react readily with GaBr3, GaCl3 and BBr3 to produce high yields of the previously reported Br2GaN3, Cl2GaN 3 and Br2BN3, respectively. The latter is shown to possess a trimeric molecular structure in which the α-nitrogen of the azide group bridges the boron atoms to form cyclohexane-like B3N 3 rings.

Original languageEnglish (US)
Pages (from-to)451-459
Number of pages9
JournalApplied Organometallic Chemistry
Volume22
Issue number8
DOIs
StatePublished - Aug 2008

Fingerprint

Nitrides
Azides
Crystalline materials
Derivatives
Fabrication
Sodium Azide
Boron
Graphite
Cyanides
Cyclohexane
Polymorphism
Optoelectronic devices
Refractory materials
Molecular structure
Solar cells
Nitrogen
Heating
Thin films
Atoms
Molecules

Keywords

  • Arsenic, silicon
  • Azides
  • Cyanides
  • Framework solids
  • GaAsN semiconductors

ASJC Scopus subject areas

  • Chemistry (miscellaneous)
  • Inorganic Chemistry
  • Bioengineering
  • Materials Chemistry

Cite this

Synthesis and properties of N3 and CN delivery compounds and related precursors for nitride and ceramic fabrication. / Tice, Jesse B.; Ritter, C. J.; Chizmeshya, Andrew; Forrest, Brandon; Torrison, Levi; Groy, T. L.; Kouvetakis, John.

In: Applied Organometallic Chemistry, Vol. 22, No. 8, 08.2008, p. 451-459.

Research output: Contribution to journalArticle

Tice, Jesse B. ; Ritter, C. J. ; Chizmeshya, Andrew ; Forrest, Brandon ; Torrison, Levi ; Groy, T. L. ; Kouvetakis, John. / Synthesis and properties of N3 and CN delivery compounds and related precursors for nitride and ceramic fabrication. In: Applied Organometallic Chemistry. 2008 ; Vol. 22, No. 8. pp. 451-459.
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abstract = "The simple azido and cyano compounds Cl2AsN3, Br 2AsN3, (C6H5)SiH2N 3, (C6H5)SiH2CN and p-(tolyl)SiH2CN have been prepared for the first time by metathesis reactions involving the corresponding halides and NaN3, LiN 3 and LiCN. These compounds represent a highly reactive and efficient family of delivery reagents for the preparation of N3 and CN molecular precursors to bulk ceramics and nitride thin films. They are isolated as low volatility liquids and characterized by spectroscopic methods and chemical analysis. Ab initio simulations were used to elucidate the structural and vibrational properties of the simpler, fully inorganic Cl 2AsN3 and Br2AsN2 species. This theoretical treatment was extended to include the hypothetical H 2AsN3 and HClAsN3 derivatives which are particularly desirable as single-source low-temperature As-N sources for the formation of highly sought after, metastable GaAs1-xNx materials for solar cell applications. The practical utility of the title molecules is also demonstrated by synthesizing several representative compounds of B, Be, Ga and Al, which are of interest for the development of open frameworks, optoelectronic nitrides and refractory B-C-N hybrids. The cyanide derivatives (C6H5)SiH2CN and p-(tolyl)SiH 2CN react readily with Be and B halides to yield crystalline Be(CN)2 and amorphous B-C-N. The latter is crystallized upon heating to form graphite-like polymorphs with homogeneous nanoscale morphologies. The azide derivatives Cl2AsN3, Br2AsN3 and (C6H5)SiH2N3 react readily with GaBr3, GaCl3 and BBr3 to produce high yields of the previously reported Br2GaN3, Cl2GaN 3 and Br2BN3, respectively. The latter is shown to possess a trimeric molecular structure in which the α-nitrogen of the azide group bridges the boron atoms to form cyclohexane-like B3N 3 rings.",
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T1 - Synthesis and properties of N3 and CN delivery compounds and related precursors for nitride and ceramic fabrication

AU - Tice, Jesse B.

AU - Ritter, C. J.

AU - Chizmeshya, Andrew

AU - Forrest, Brandon

AU - Torrison, Levi

AU - Groy, T. L.

AU - Kouvetakis, John

PY - 2008/8

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N2 - The simple azido and cyano compounds Cl2AsN3, Br 2AsN3, (C6H5)SiH2N 3, (C6H5)SiH2CN and p-(tolyl)SiH2CN have been prepared for the first time by metathesis reactions involving the corresponding halides and NaN3, LiN 3 and LiCN. These compounds represent a highly reactive and efficient family of delivery reagents for the preparation of N3 and CN molecular precursors to bulk ceramics and nitride thin films. They are isolated as low volatility liquids and characterized by spectroscopic methods and chemical analysis. Ab initio simulations were used to elucidate the structural and vibrational properties of the simpler, fully inorganic Cl 2AsN3 and Br2AsN2 species. This theoretical treatment was extended to include the hypothetical H 2AsN3 and HClAsN3 derivatives which are particularly desirable as single-source low-temperature As-N sources for the formation of highly sought after, metastable GaAs1-xNx materials for solar cell applications. The practical utility of the title molecules is also demonstrated by synthesizing several representative compounds of B, Be, Ga and Al, which are of interest for the development of open frameworks, optoelectronic nitrides and refractory B-C-N hybrids. The cyanide derivatives (C6H5)SiH2CN and p-(tolyl)SiH 2CN react readily with Be and B halides to yield crystalline Be(CN)2 and amorphous B-C-N. The latter is crystallized upon heating to form graphite-like polymorphs with homogeneous nanoscale morphologies. The azide derivatives Cl2AsN3, Br2AsN3 and (C6H5)SiH2N3 react readily with GaBr3, GaCl3 and BBr3 to produce high yields of the previously reported Br2GaN3, Cl2GaN 3 and Br2BN3, respectively. The latter is shown to possess a trimeric molecular structure in which the α-nitrogen of the azide group bridges the boron atoms to form cyclohexane-like B3N 3 rings.

AB - The simple azido and cyano compounds Cl2AsN3, Br 2AsN3, (C6H5)SiH2N 3, (C6H5)SiH2CN and p-(tolyl)SiH2CN have been prepared for the first time by metathesis reactions involving the corresponding halides and NaN3, LiN 3 and LiCN. These compounds represent a highly reactive and efficient family of delivery reagents for the preparation of N3 and CN molecular precursors to bulk ceramics and nitride thin films. They are isolated as low volatility liquids and characterized by spectroscopic methods and chemical analysis. Ab initio simulations were used to elucidate the structural and vibrational properties of the simpler, fully inorganic Cl 2AsN3 and Br2AsN2 species. This theoretical treatment was extended to include the hypothetical H 2AsN3 and HClAsN3 derivatives which are particularly desirable as single-source low-temperature As-N sources for the formation of highly sought after, metastable GaAs1-xNx materials for solar cell applications. The practical utility of the title molecules is also demonstrated by synthesizing several representative compounds of B, Be, Ga and Al, which are of interest for the development of open frameworks, optoelectronic nitrides and refractory B-C-N hybrids. The cyanide derivatives (C6H5)SiH2CN and p-(tolyl)SiH 2CN react readily with Be and B halides to yield crystalline Be(CN)2 and amorphous B-C-N. The latter is crystallized upon heating to form graphite-like polymorphs with homogeneous nanoscale morphologies. The azide derivatives Cl2AsN3, Br2AsN3 and (C6H5)SiH2N3 react readily with GaBr3, GaCl3 and BBr3 to produce high yields of the previously reported Br2GaN3, Cl2GaN 3 and Br2BN3, respectively. The latter is shown to possess a trimeric molecular structure in which the α-nitrogen of the azide group bridges the boron atoms to form cyclohexane-like B3N 3 rings.

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KW - Azides

KW - Cyanides

KW - Framework solids

KW - GaAsN semiconductors

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