Distinct fluorescence state, mechanofluorochromism of terpyridine conjugated fluorophores and the reusable sensing of nitroaromatics in aqueous medium

Terpyridine (TP) integrated with tetraphenylethylene (TPE-TP), pyrene (Py-TP) and triphenylamine (TPA-TP) exhibited structure controlled molecular packing and distinct fluorescence in the solid state. TPE-TP exhibited infinite aromatic pMIDLINE HORIZONTAL ELLIPSISp stacking between terpyridine units, Py-TP produced an isolated pyrene dimer, and TPA-TP displayed helical assembly via weak intermolecular H-bonding in the crystal lattice. The different molecular assembly of TPE-TP, TPA-TP and Py-TP produced a locally excited (LE) state, charge transfer (CT) state and excimeric emission at 460, 520 and 568 nm, respectively, in the solid state. Interestingly, the different molecular packing of TPE-TP, Py-TP and TPA-TP produced varied mechanofluorochromism. TPA-TP exhibited on-off reversible fluorescence switching upon mechanical crushing and heating, whereas TPE-TP and Py-TP displayed switching between two fluorescence states but in opposite directions. Crushing caused red shift of emission in TPE-TP and blue shift in Py-TP. Both TPA-TP and Py-TP showed strong fluorescence in solution and crystalline states, but TPE-TP showed typical aggregation induced emission (AIE). Further, Py-TP and TPE-TP showed selective fluorescence sensing of picric acid in solution and solid matrix, respectively. TPA-TP exhibited sensing of nitroaromatics both in solution as well as in the solid state. Solid state fluorescence of TPA-TP and TPE-TP was further utilized for fabricating PVA polymer composite thin films and demonstrated reusable fluorescence sensing of nitroaromatics in aqueous medium. The PVA-fluorophore composite film exhibited clear fluorescence quenching upon immersing the thin film into 10(-7) M picric acid. Thus, the present study demonstrates the role of molecular structure in developing stimuli-responsive fluorescence materials and reusable sensors.

Automated summary

Terpyridine (TP) integrated with TPE-TP, Py-TP, and TPA-TP exhibited structure-controlled molecular packing and distinct fluorescence properties in the solid state. Different molecular assembly produced varied mechanofluorochromism and fluorescence sensing capabilities for picric acid and nitroaromatics.