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.