Solid-State 13C NMR Study of Chiral Twisted Conformation Attributable to Chirality in Smectic Phases of Achiral Banana-Shaped Molecules

Solid-state 13C NMR measurements were made for the B2 and B4 phases of the achiral banana-shaped molecule, P-14-O-PIMB, which exhibits a direct transformation from the B2 phase to the B4 phase. In both phases, an NMR resonance signal assigned to carbonyl carbons of the ester linkages appears as doublet peaks, showing that the two carbonyl carbons are circumstanced in different electronic environments on the NMR time scale. The chemical shifts of the two peaks are 165.6 and 163.9 ppm in the B2 phase, and these values are not changed in the transformation to the low-temperature B4 phase. To explain this distinct splitting of the carbonyl carbon signal, we take three assumptions into account:  (1) the molecules are accommodated in the unique phase, but the conformational exchange between two states takes place slowly; (2) the two side wings of each molecule experience fast interconformational jumps, but their “average conformer” is different, thus giving two different peaks in the spectra; and (3) the indivi...