Work

Point‐to‐Axis Optical Activity Induction in Extended, Sterically Congested Chromophoric Systems

Year: 2025

Type: article

Abstract: The readily available, modular, and electronic circular dichroism (ECD)‐silent derivatives of terephthalaldehyde (the probes) have exhibited an induced optical activity (OA) upon condensation with chiral primary amines. The central unit of the probe serves as an amine binder by forming imine bonds and is flanked by two extended chromophoric units (the wings). Modification of the wings by diphenylamine or carbazole units affects the sterical and spectroscopic properties of the probes. An increase in sterical congestion within the probe core results in a change in the mechanism of OA induction. In the more congested systems, the point‐to‐axial chirality transmission from the chiral amine (the inducer) to the chromophoric system leads to the adaptation of helical conformation by “the wings” and the appearance of nonzero Cotton effects in the low‐energy part of the ECD spectrum. However, the sterically congested probes are sensitive to the chirality of the inducers but relatively indifferent to the differences in their structure. Thus, the chirality of the inducers triggers conformational change toward the thermodynamically preferred conformational diastereoisomer due to the probe's −1 to +1 operation scheme.

Source: European Journal of Organic Chemistry

DOI: 10.1002/ejoc.202500461

Authors: Klaudia Chuchracka, Agnieszka Czapik, Marcin Kwit, Paweł Skowronek

Institution: Adam Mickiewicz University in Poznań

Language: English

Topic: Molecular spectroscopy and chirality

Subfield: Spectroscopy

Field: Chemistry

Domain: Physical Sciences

Open Access status: bronze

Funder: Narodowe Centrum Nauki

Award: G8191940224