Syntheses, X‐ray Crystal Structures, and Raman Spectra of Self‐Assembled XeO3 Chain and Network Complexes of Polytopic sp2‐ and sp3‐Nitrogen Bases

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.