Syntheses, X‐ray Crystal Structures, and Raman Spectra of Self‐Assembled XeO3 Chain and Network Complexes of Polytopic sp2‐ and sp3‐Nitrogen Bases
- 1Department of Chemistry McMaster University Hamilton Ontario Canada
Abstract
Xenon trioxide was used as a template to synthesize a structurally diverse series of self‐assembled network complexes. Reactions of XeO3 in aqueous or CH3CN solutions with the polytopic nitrogen bases, 2,2′‐bipyridine (2,2′‐bipy), 1,10‐phenanthroline (1,10‐phen), 4,4′‐bipyridine (4,4′‐bipy), hexamethylenetetramine (HMTA), and 1,4‐diazabicyclo[2.2.2]octane (DABCO) yield 1‐, 2‐, and 3‐D supramolecular XeO3 complexes. The low‐temperature X‐ray crystal structures of room‐temperature‐stable O3Xe(2,2′‐bipy), O3Xe(1,10‐phen), and O3Xe(4,4′‐bipy), consist of Xe‐‐‐O σ‐hole‐bonded ‐(‐O═Xe(O2)‐‐)‐∞ chains that coordinate through Xe‐‐‐N σ–hole bonds. Shock‐insensitive O3Xe(HMTA)(H2O) is crosslinked by ‐(‐Xe(O2)O‐‐‐HO(H)‐‐)‐∞ chains that are Xe‐‐‐N and Xe‐‐‐O coordinated to HMTA and H2O to give 3‐D networks, whereas highly shock‐sensitive and explosive (O3Xe)2(HMTA) forms 3‐D networks in which ‐(‐O═Xe(O2)‐‐)‐∞ chains couple to form layers that are Xe‐‐‐N coordinated to HMTA. Reaction of DABCO with XeO3 in HF(aq) yields stable [HDABCO]2[(μ‐FXeO3)2]·H2O and [H2DABCO][F][H2F3] salts. The XeO3 moieties of [(μ‐FXeO3)2]2− form crosslinked ‐(‐HOH‐‐[‐O═Xe(O)2(μ‐F)2(O2)Xe═O‐]‐‐)‐∞ chains that are Xe‐‐‐N coordinated to [HDABCO]+. The XeO3 complexes provide examples of Xe(VI)‐‐‐N σ–hole bonds with sp2‐ and sp3‐hybridized polytopic N‐bases, where O3Xe(2,2′‐bipy) and O3Xe(1,10‐phen) are unique examples of chelated noble‐gas centers, and O3Xe(HMTA)(H2O) is a rare example of a Xe‐‐‐O σ–hole bonded noble‐gas hydrate.
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BibTeX
@article{goettel2026syntheses,
title = {{Syntheses, X‐ray Crystal Structures, and Raman Spectra of Self‐Assembled XeO3 Chain and Network Complexes of Polytopic sp2‐ and sp3‐Nitrogen Bases}},
author = {James T. Goettel and Hélène P. A. Mercier and Gary J. Schrobilgen},
journal = {Angewandte Chemie (International Ed. in English)},
year = {2026},
month = sep,
doi = {10.1002/anie.6506301},
url = {https://doi.org/10.1002/anie.6506301},
note = {CC BY-NC-ND 4.0},
}
RIS
TY - JOUR
TI - Syntheses, X‐ray Crystal Structures, and Raman Spectra of Self‐Assembled XeO3 Chain and Network Complexes of Polytopic sp2‐ and sp3‐Nitrogen Bases
AU - James T. Goettel
AU - Hélène P. A. Mercier
AU - Gary J. Schrobilgen
PY - 2026
DA - 2026/09/16
JO - Angewandte Chemie (International Ed. in English)
DO - 10.1002/anie.6506301
UR - https://doi.org/10.1002/anie.6506301
AB - Xenon trioxide was used as a template to synthesize a structurally diverse series of self‐assembled network complexes. Reactions of XeO3 in aqueous or CH3CN solutions with the polytopic nitrogen bases, 2,2′‐bipyridine (2,2′‐bipy), 1,10‐phenanthroline (1,10‐phen), 4,4′‐bipyridine (4,4′‐bipy), hexamethylenetetramine (HMTA), and 1,4‐diazabicyclo[2.2.2]octane (DABCO) yield 1‐, 2‐, and 3‐D supramolecular XeO3 complexes. The low‐temperature X‐ray crystal structures of room‐temperature‐stable O3Xe(2,2′‐bipy), O3Xe(1,10‐phen), and O3Xe(4,4′‐bipy), consist of Xe‐‐‐O σ‐hole‐bonded ‐(‐O═Xe(O2)‐‐)‐∞ chains that coordinate through Xe‐‐‐N σ–hole bonds. Shock‐insensitive O3Xe(HMTA)(H2O) is crosslinked by ‐(‐Xe(O2)O‐‐‐HO(H)‐‐)‐∞ chains that are Xe‐‐‐N and Xe‐‐‐O coordinated to HMTA and H2O to give 3‐D networks, whereas highly shock‐sensitive and explosive (O3Xe)2(HMTA) forms 3‐D networks in which ‐(‐O═Xe(O2)‐‐)‐∞ chains couple to form layers that are Xe‐‐‐N coordinated to HMTA. Reaction of DABCO with XeO3 in HF(aq) yields stable [HDABCO]2[(μ‐FXeO3)2]·H2O and [H2DABCO][F][H2F3] salts. The XeO3 moieties of [(μ‐FXeO3)2]2− form crosslinked ‐(‐HOH‐‐[‐O═Xe(O)2(μ‐F)2(O2)Xe═O‐]‐‐)‐∞ chains that are Xe‐‐‐N coordinated to [HDABCO]+. The XeO3 complexes provide examples of Xe(VI)‐‐‐N σ–hole bonds with sp2‐ and sp3‐hybridized polytopic N‐bases, where O3Xe(2,2′‐bipy) and O3Xe(1,10‐phen) are unique examples of chelated noble‐gas centers, and O3Xe(HMTA)(H2O) is a rare example of a Xe‐‐‐O σ–hole bonded noble‐gas hydrate.
SN - 1433-7851
SN - 1521-3773
ER -