RESUMO
N,N'-Diarylsquaramide and N,N'-dialkylsquaramide are conformationally stable linkers with extended (trans, trans) and folded (cis, cis) structures, respectively, independently of external conditions. Here, we show that N-monomethylated N,N'-diarylsquaramides generally take a (trans, cis) structure in the crystal but show a solvent-dependent conformational equilibrium in solution. In particular, the stable conformer of N-methyl-N,N'-bis(1-naphthyl)squaramide (1f) changes depending upon the solvent. Thus, aromatic N-monomethylated squaramides could find application as components of environment-responsive molecular switches.
RESUMO
Squaramide is a highly rigid four-membered ring system bearing two carbonyl and two amino groups, and its derivatives have found applications in many fields. We synthesized several N,N'-dimethylated oligosquaramides linked via phenyl groups, and investigated their structures in the crystalline state and in solution. Compounds 1, 2 (bissquaramides), and 13 (trissquaramide) exist as folded structures in the crystalline state, in which the aromatic rings are located in a face-to-face position. In their multilayered structures, the benzene rings are more nearly parallel and are closer to each other, compared with those in N,N'-dimethylated oligoureas. Individual molecules of meta-connected compounds 2 and 13 show a helical structure with all-R or all-S axis chirality, but afford only racemic crystals. The NMR spectra indicated that these compounds retain well-ordered folded structures in solution. The unique steric and electronic properties of N,N'-dimethylated squaramide can provide access to novel functional aromatic multilayered and helical foldamers.