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Title: Intermolecular Stabilization of 3,3'-Diamino-4,4'-azoxyfurazan (DAAF) Compressed to 20 GPa

Abstract

The room temperature stability of 3,3'-diamino-4,4'-azoxyfurazan (DAAF) has been investigated using synchrotron far-infrared, mid-infrared, Raman spectroscopy, and synchrotron X-ray diffraction (XRD) up to 20 GPa. The as-loaded DAAF samples exhibited subtle pressure-induced ordering phenomena (associated with positional disorder of the azoxy “O” atom) resulting in doubling of the a-axis, to form a superlattice similar to the low-temperature polymorph. Neither high pressure synchrotron XRD, nor high pressure infrared or Raman spectroscopies indicated the presence of structural phase transitions up to 20 GPa. Compression was accommodated in the unit cell by a reduction of the c-axis between the planar DAAF layers, distortion of the β-angle of the monoclinic lattice, and an increase in intermolecular hydrogen bonding. Changes in the ring and -NH2 deformation modes and increased intermolecular hydrogen bonding interactions with compression suggest molecular reorganizations and electronic transitions at ~5 GPa and ~10 GPa that are accompanied by a shifting of the absorption band edge into the visible. A fourth-order Birch–Murnaghan fit to the room temperature isotherm afforded an estimate of the zero-pressure isothermal bulk modulus, K0 = 12.4 ± 0.6 GPa and its pressure derivative K0' = 7.7 ± 0.3.

Authors:
; ; ; ; ;
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1354409
Report Number(s):
BNL-112926-2016-JA
Journal ID: ISSN 1089-5639
DOE Contract Number:  
SC00112704
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 118; Journal Issue: 31; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Chellappa, Raja S., Dattelbaum, Dana M., Coe, Joshua D., Velisavljevic, Nenad, Stevens, Lewis L., and Liu, Zhenxian. Intermolecular Stabilization of 3,3'-Diamino-4,4'-azoxyfurazan (DAAF) Compressed to 20 GPa. United States: N. p., 2014. Web. doi:10.1021/jp504935g.
Chellappa, Raja S., Dattelbaum, Dana M., Coe, Joshua D., Velisavljevic, Nenad, Stevens, Lewis L., & Liu, Zhenxian. Intermolecular Stabilization of 3,3'-Diamino-4,4'-azoxyfurazan (DAAF) Compressed to 20 GPa. United States. https://doi.org/10.1021/jp504935g
Chellappa, Raja S., Dattelbaum, Dana M., Coe, Joshua D., Velisavljevic, Nenad, Stevens, Lewis L., and Liu, Zhenxian. 2014. "Intermolecular Stabilization of 3,3'-Diamino-4,4'-azoxyfurazan (DAAF) Compressed to 20 GPa". United States. https://doi.org/10.1021/jp504935g.
@article{osti_1354409,
title = {Intermolecular Stabilization of 3,3'-Diamino-4,4'-azoxyfurazan (DAAF) Compressed to 20 GPa},
author = {Chellappa, Raja S. and Dattelbaum, Dana M. and Coe, Joshua D. and Velisavljevic, Nenad and Stevens, Lewis L. and Liu, Zhenxian},
abstractNote = {The room temperature stability of 3,3'-diamino-4,4'-azoxyfurazan (DAAF) has been investigated using synchrotron far-infrared, mid-infrared, Raman spectroscopy, and synchrotron X-ray diffraction (XRD) up to 20 GPa. The as-loaded DAAF samples exhibited subtle pressure-induced ordering phenomena (associated with positional disorder of the azoxy “O” atom) resulting in doubling of the a-axis, to form a superlattice similar to the low-temperature polymorph. Neither high pressure synchrotron XRD, nor high pressure infrared or Raman spectroscopies indicated the presence of structural phase transitions up to 20 GPa. Compression was accommodated in the unit cell by a reduction of the c-axis between the planar DAAF layers, distortion of the β-angle of the monoclinic lattice, and an increase in intermolecular hydrogen bonding. Changes in the ring and -NH2 deformation modes and increased intermolecular hydrogen bonding interactions with compression suggest molecular reorganizations and electronic transitions at ~5 GPa and ~10 GPa that are accompanied by a shifting of the absorption band edge into the visible. A fourth-order Birch–Murnaghan fit to the room temperature isotherm afforded an estimate of the zero-pressure isothermal bulk modulus, K0 = 12.4 ± 0.6 GPa and its pressure derivative K0' = 7.7 ± 0.3.},
doi = {10.1021/jp504935g},
url = {https://www.osti.gov/biblio/1354409}, journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
issn = {1089-5639},
number = 31,
volume = 118,
place = {United States},
year = {2014},
month = {7}
}