Control of Relative Positions of Electron-Donor and Electron-Acceptor Molecules in Charge-Transfer Complexes for Luminescent Property Modulation

Chemistry. 2024 Jan 22;30(5):e202302965. doi: 10.1002/chem.202302965. Epub 2023 Dec 4.

Abstract

Charge-transfer complexes can exhibit various physical properties that depend on the relative positions of electron-donor and electron-acceptor molecules. Several studies have investigated the relationship between the relative positions of electron-donor and electron-acceptor molecules and their luminescence properties. However, elucidating the correlation between the relative positions and detailed luminescence processes without changing the molecular structures has not been explored. Herein, we report control of the relative position based on charge-assisted hydrogen bonds between sulfo and amino groups and on alkylamines' steric factors, and report concomitant modulation of the luminescent properties. Six charge-transfer complexes were prepared from anthracene-2,6-disulfonic acid and 1,2,4,5-tetracyanobenzene as electron-donor and electron-acceptor molecules, and various alkylamines. Different alkylamines' steric factors drastically and precisely changed the relative positions of the electron-donor and electron-acceptor molecules without changing their molecular structures. Consequently, the six crystals exhibited maximum emission wavelengths from 543 to 624 nm and different luminescence processes.

Keywords: charge-transfer complexes; cocrystals; luminescence modulation; luminescent properties; relative positions.