Near-IR absorbing 1,1,4,4-tetracyanobutadiene-functionalized phenothiazine sulfones

Abstract

Triphenylamine (TPA) substituted π-conjugated chromophores TPA1-TPA5 were designed and synthesized via Pd-catalysed Sonogashira cross-coupling followed by [2 + 2] cycloaddition-retroelectrocyclization (CA-RE) reactions. The effects of acceptor 1,1,4,4-tetracyanobutadiene (TCBD) and cyclohexa-2,5-diene-1,4-diylidene-expanded TCBD (DCNQ) units in the photophysical studies and the HOMO-LUMO energy levels of the phenothiazine sulfones TPA1-TPA5 were evaluated. The absorption spectra of chromophores TPA4 and TPA5 show a significant change due to the incorporation of DCNQ units, resulting in bathochromically shifted broad absorption in the NIR region. The photophysical studies revealed that DCNQ-based chromophores TPA4 and TPA5 have a better D-A interaction than the TCBD functionalized TPA2 and TPA3. Density functional theory calculations and electrochemical studies were performed to examine the molecular geometry and frontier energy levels of the sulfone-based chromophores. Systematic structural modification of the chromophore TPA1 modulated the electrochemical properties and successively tuned the energy gaps for TPA2-TPA5. The theoretically estimated HOMO-LUMO gaps for TPA1-TPA5 exhibit good agreement with the experimental data calculated from the electrochemical studies. The chromophore TPA1 exhibits solvatochromism and aggregation-induced emission (AIE) behavior owing to the emission in the solid state. © 2023 The Royal Society of Chemistry.