Syntheses, X‐ray Crystal Structures, and Raman Spectra of Self‐Assembled XeO 3 Chain and Network Complexes of Polytopic sp 2 ‐ and sp 3 ‐Nitrogen Bases

ABSTRACT Xenon trioxide was used as a template to synthesize a structurally diverse series of self‐assembled network complexes. Reactions of XeO 3 in aqueous or CH 3 CN 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 XeO 3 complexes. The low‐temperature X‐ray crystal structures of room‐temperature‐stable O 3 Xe(2,2′‐bipy), O 3 Xe(1,10‐phen), and O 3 Xe(4,4′‐bipy), consist of Xe‐‐‐O σ‐hole‐bonded ‐(‐O═Xe(O 2 )‐‐)‐ ∞ chains that coordinate through Xe‐‐‐N σ–hole bonds. Shock‐insensitive O 3 Xe(HMTA)(H 2 O) is crosslinked by ‐(‐Xe(O 2 )O‐‐‐HO(H)‐‐)‐ ∞ chains that are Xe‐‐‐N and Xe‐‐‐O coordinated to HMTA and H 2 O to give 3‐D networks, whereas highly shock‐sensitive and explosive (O 3 Xe) 2 (HMTA) forms 3‐D networks in which ‐(‐O═Xe(O 2 )‐‐)‐ ∞ chains couple to form layers that are Xe‐‐‐N coordinated to HMTA. Reaction of DABCO with XeO 3 in HF(aq) yields stable [HDABCO] 2 [( μ ‐FXeO 3 ) 2 ]·H 2 O and [H 2 DABCO][F][H 2 F 3 ] salts. The XeO 3 moieties of [( μ ‐FXeO 3 ) 2 ] 2− form crosslinked ‐(‐HOH‐‐[‐O═Xe(O) 2 ( μ ‐F) 2 (O 2 )Xe═O‐]‐‐)‐ ∞ chains that are Xe‐‐‐N coordinated to [HDABCO] + . The XeO 3 complexes provide examples of Xe(VI)‐‐‐N σ–hole bonds with sp 2 ‐ and sp 3 ‐hybridized polytopic N‐bases, where O 3 Xe(2,2′‐bipy) and O 3 Xe(1,10‐phen) are unique examples of chelated noble‐gas centers, and O 3 Xe(HMTA)(H 2 O) is a rare example of a Xe‐‐‐O σ–hole bonded noble‐gas hydrate.