2 research outputs found
Positional Isomerism and Steric Effects in the Self-Assemblies of Phenylene Bis-Monothiooxalamides
The
potential interplay of steric and substitution pattern effects
of the monothiooxalamide side arms on the structure, conformational
features, and self-assembly of a series of phenylene bis-monothiooxalamides
was investigated. Herein we have demonstrated that phenylene bis-monothiooxalamides
self-associate in the solid state, through intermolecular hydrogen
bonding as <i>meso</i>-helices when the thioamide NR group
is <sup><i>s</i></sup>Bu and through dispersive CO路路路CX
(X = O, S, 蟺), S路路路S, and C鈥揌路路路S
interactions when R is <sup><i>t</i></sup>Bu, independently
from the substitution pattern in the phenyl ring. The helical structures
are exclusively developed through N<sub>CS</sub>H路路路O
hydrogen bonding. The steric strain imposed by the <i>ortho</i>-substitution pattern has the effect of moving both monothiooxalyl
units out of the phenyl plane enabling dimerization through strong
N<sub>CO</sub>H路路路O intermolecular hydrogen bonds and
promotes the formation of <i>meso</i>-helices. The steric
demand of the thioamide NR group rules the conformation adopted by <i>meta</i>-substituted derivatives and the self-association arrangement
of <i>para</i>-substituted derivatives. Infrared data support
the blue-shifted nature of the N<sub>CS</sub>H路路路O
hydrogen bond. NMR data in solution agree with the extensive intramolecular
hydrogen bonding scheme. Results are supported by density functional
theory theoretical calculations. Monothiooxalamide unit offers considerable
potential as a key moiety for crystal engineering