A New 'Off-On' System Based on Core-Substituted Naphthalene Diimide with Dimethylamine for Reversible Acid-Base...

A new 'Off-On' system designed and synthesised by functionalisation of a naphthalene diimide (NDI) core with dimethylamine produces 4,9-bis(dimethylamino)-2,7-dioctylbenzo[lmn][3,8]-phenanthroline-1,3,6,8-(2H,7H)-tetraone, abbreviated as DDPT (1). DDPT 1 was synthesised using a simple strategy, namely aromatic nucleophilic substitution using Br₂ -NDI with dimethylamine at 110 °C. DDPT was characterized by ¹ H and ¹³ C NMR spectroscopy, ESI mass spectrometry and elemental analysis. DDPT 1 was then used for optical studies through protonation of its dimethylamine core with trifluoroacetic acid (TFA), blue-shifting the absorption band from 600 nm to 545 nm in solution. Interestingly, the fluorescence of DDPT 1 is weak in solution with a quantum yield Φ=0.09, which is significantly enhanced to Φ=0.78 upon addition of TFA. The limit of detection (LOD) was determined to 2.77 nm. Furthermore, DDPT 1 can be used for naked eyed detection not only under UV light (365 nm) but also using visible light, as clear changes can be clearly seen upon addition of TFA. The binding constant of DDPT was calculated to 2.1×10^-3  m^-1 . Importantly, DDPT 1 showed reversible switching by alternative addition of acid (TFA) and base (triethylamine) without loss of activity. Immobilised on paper, DDPT 1 can be used for strip-test sensing in which the colour changes from blue to reddish when expose to TFA vapours and reverse in the presence of triethylamine vapours.