TD-DFT investigation on anion recognition mechanism of anthraldehyde-based fluorescent thiosemicarbazone derivatives

The mechanism of host–guest interaction of receptors towards fluoride ion has been investigated using computational methods. To distinguish the effect of aromaticity in host–guest interaction, we investigated unsubstituted (ATSC) and phenyl-substituted (APTSC) anthracene thiosemicarbazones towards different ions. In the ground state of receptor-fluoride complex, the added fluoride ion made hydrogen bond through N − H … F … H − N, whereas the intramolecular hydrogen bonding was through F − H … N in the excited state of receptor-fluoride complex. Experimental absorption and emission spectra were well reproduced by the calculated vertical excitation energies. The transition state (TS) calculations were performed to understand the thermodynamic features and mechanism of host–guest interaction. The natural bond orbital analyses show that the second perturbation energy for donor–acceptor interaction of F − with hydrogen is more than 300 kcal/mol −1 at the excited state of receptor-fluoride complex, which indicates the strong single bond between fluoride and hydrogen atom. The PES scan confirms that deprotonation took place at the excited state of receptor-fluoride complex. The results indicate the excited-state proton transfer (ESPT) process from N–H group nearby the anthracene moiety. The APTSC is a better chemosensor than ATSC. This infers that the aromaticity will increase the efficiency of fluorescence receptor towards fluoride ion. Graphical abstract A schematic representation of sensing mode of anthracene-based thiosemicarbazones toward fluoride ion. The fluoride ion first makes a hydrogen bond with NH proton nearby anthracene moiety. The excited state proton transfer mechanism was confirmed by PES and NBO studies.