Salen-indium/triarylborane triads: synthesis and ratiometric emission-colour changes by fluoride ion binding

Salen-based indium triads, [{(3-tBu)2-(5-Mes2B)2-salen}In-Me] (1) and [{(3-tBu)2-(5-Mes2Bphenyl)2-salen}In-Me] (2), bearing triarylborane (TAB) units were prepared and fully characterised by NMR spectroscopy and elemental analysis. The major absorption bands of 1 and 2 appeared in the region centred at 347 nm and 374 nm, respectively, and the intense emission spectra were observed in the sky blue (λem = 491 nm for 1) and bluish-green (λem = 498 nm for 2) regions, respectively. The solvatochromism effects in various organic solvents and computational calculation results strongly suggested that these absorption and emission features are mainly attributed to intramolecular charge transfer (ICT) transitions between the salen ligand moieties and the TAB units. Furthermore, UV-vis and photoluminescence (PL) titration experiments by the addition of fluoride anions demonstrated ratiometric quenching patterns in both the absorption and emission spectra, indicating that binding of the fluoride anion to the boron centres interrupts these ICT transitions in each compound. Interestingly, both triads exhibited a gradual red-shifted response in each emission spectrum upon the addition of the fluoride anions, resulting in a dramatic colour-change to yellow. The computational calculation results of the S1 states revealed that these emission-colour change properties arise from the elevation of HOMO levels, which are mainly localised on the TAB moieties, resulting from the fluoride anion binding to the borane centres.