Host behaviour of related compounds, TETROL and DMT, in the presence of two different classes of aromatic guest compounds

Abstract

The host potential of two closely-related compounds, TETROL [(+)-(2R,3R)-1,1–4,4-tetraphenylbutane-1,2,3,4-tetraol] and DMT [(−)-(2R,3R)-2,3-dimethoxy-1,1,4,4-tetraphenylbutane-1,4-diol], were compared when recrystallized from two different classes of guests, namely toluene, ethylbenzene, cumene and aniline, N-methylaniline, N,N-dimethylaniline. TETROL formed complexes with only aniline and N-methylaniline (host:guest ratios, 2:3 and 2:4), while DMT included all six guests with a consistent ratio (2:1). Aniline competition experiments showed that TETROL preferred aniline (67%), followed by N-methyl- (29%) and N,N-dimethyl- (4%) aniline; surprisingly, this order was exactly reversed for DMT [N,N-dimethylaniline (62%) > N-methylaniline (32%) > aniline (6%)]. Crystal diffraction analyses revealed that TETROL formed stabilizing hydrogen bonds with guests, behaving as both donor and, for the first time, acceptor (in 2TETROL∙4N-methylaniline). DMT did not form bonds of this type with any guests. Furthermore, the host packing was isostructural for all DMT complexes but was guest-dependent for TETROL. Thermal analyses showed that complex stabilities correlated precisely with the host preferences.