Theoretical
and Spectroscopic Analysis of <i>N</i>,<i>N</i>′‑Diphenylurea and <i>N</i>,<i>N</i>′‑Dimethyl‑<i>N</i>,<i>N</i>′‑diphenylurea Conformations
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Abstract
Structural organization of macromolecules
is highly dependent on
the conformational propensity of the monomer units. Our goal is to
systematically quantify differences in the conformational propensities
of aromatic oligourea foldamer units. Specifically, we investigate
the conformational propensities of <i>N</i>,<i>N</i>′-diphenylurea and <i>N</i>,<i>N</i>′-dimethyl-<i>N</i>,<i>N</i>′-diphenylurea in different media
using a combination of theoretical methods, and infrared and nuclear
magnetic resonance spectroscopies. Our results show variation in the
conformational behavior upon adding methyl substituents on <i>N</i>,<i>N</i>′-diphenylurea, and varying the
environments surrounding the compounds. Our energetic analyses and
conformational distributions in the gas phase show predominance of
the <i>cis</i>–<i><i>trans</i></i> and <i>trans</i>–<i>trans</i> conformations
for <i>N</i>,<i>N</i>′-diphenylurea, while <i>cis</i>–<i>cis</i> conformation is favored
for <i>N</i>,<i>N</i>′-dimethyl-<i>N</i>,<i>N</i>′-diphenylurea. In solution,
our results support the <i>trans</i>–<i>trans</i> conformer as the predominant conformer for <i>N</i>,<i>N</i>′-diphenylurea, whereas the <i>cis</i>–<i>cis</i> and <i>cis</i>–<i>trans</i> forms are favored in <i>N</i>,<i>N</i>′-dimethyl-<i>N</i>,<i>N</i>′-diphenylurea. <i>N</i>,<i>N</i>′-Dimethyl-<i>N</i>,<i>N</i>′-diphenylurea also exhibits a more dynamic
conformational behavior in solution, with constant fluctuations between <i>cis</i>–<i>cis</i> and <i>cis</i>–<i>trans</i> conformations. Our detailed quantitative
analyses are an important aspect in fine-tuning desired conformations
and dynamic properties of this class of oligomers by providing a molecular
basis for the behavior at the monomeric level