Solvatochromic and Proton-Responsive characteristics of Bi-1,3,4-Oxadiazole derivatives with symmetric dimethylamino substitution

Abstract

D-A molecules find extensive use in intelligent stimulus–response systems due to their exceptional attributes, including high sensitivity, rapid response, wide compatibility, and structural adaptability. The strength of Intramolecular Charge Transfer (ICT) plays a pivotal role in determining the performance of these devices. To enhance the ICT strength and explore new applications for D-A molecules, we meticulously designed a pair of symmetric dimethylamino-substituted bi-1,3,4-oxadiazole derivatives (DMAOXD and DMAOXDBEN). These symmetric D-A-A-D molecules, with strong electron donor terminals, displayed a modest redshift of less than 25 nm in the UV–vis absorption spectra. However, there was a significant redshift in the emission spectra (140 nm for DMAOXD and 170 nm for DMAOXDBEN) when transitioning from cyclohexane to dimethyl sulfoxide, indicating a pronounced ICT characteristic. Theoretical calculations support the idea that the dimethylaminophenyl unit serves as an electron donor in both DMAOXD and DMAOXDBEN, while the 1,3,4-oxadiazole and central benzene ring act as acceptors. The pronounced ICT characteristic observed in DMAOXD and DMAOXDBEN can be attributed to long-distance electron transfer. Additionally, it's noteworthy that the emission of DMAOXD and DMAOXDBEN solution samples can be quenched by adding trifluoroacetic acid (TFA) and restored by the addition of triethylamine (TEA). Inspired by this, a pattern created with ink samples containing DMAOXD and DMAOXDBEN can be concealed through fumigation with TFA and subsequently revealed by treating them with TEA, suggesting their potential use in data encryption.