Chiral Triphenylacetic Acid Esters: Residual Stereoisomerism and Solid-State Variability of Molecular Architectures.

Abstract

We have proven the usability and versatility of chiral triphenylacetic acid esters, compounds of high structural diversity, as chirality-sensing stereodynamic probes and as molecular tectons in crystal engineering. The low energy barrier to stereoisomer interconversion has been exploited to sense the chirality of an alkyl substituent in the esters. The structural information are cascaded from the permanently chiral alcohol (inducer) to the stereodynamic chromophoric probe through cooperative interactions. The ECD spectra of triphenylacetic acid esters are highly sensitive to very small structural differences in the inducer core. The tendencies to maximize the C–H···O hydrogen bonds, van der Waals interactions, and London dispersion forces determine the way of packing molecules in the crystal lattice. The phenyl embraces of trityl groups allowed, to some extent, the control of molecular organization in the crystal. However, the spectrum of possible molecular arrangements is very broad and depends on the type of substituent, the optical purity of the sample, and the presence of a second trityl group in the proximity. Racemates crystallize as the solid solution of enantiomers, where the trityl group acts as a protecting group for the stereogenic center. Therefore, the absolute configuration of the inducer is irrelevant to the packing mode of molecules in the crystal.