Fluorescent detection mechanism of CO-releasing molecule-3: Competition of inter-/intra-molecular hydrogen bonds.

[Display omitted] • The ESIPT of monomer PTI induces keto → enol transfer and the red-shift of fluorescent spectra. • The strengthening of intermolecular hydrogen bond hinders the occurrence of ESIPT of PTI. • The large Stokes shift of PTI is induced by hydrogen bond strengthening while not ESIPT. The fluorescent detection mechanism of 2-(4-nitro-1,3-dioxoisoindolin-2-yl) acetic acid (CORM3-green) on CO-Releasing Molecule-3 (CORM-3) is theoretically studied. Upon reaction with CORM-3, the non-fluorescent CORM3-green is transferred to the keto form of 2-(4-amino-1,3-dioxoisoindolin-2-yl)acetic acid (PTI) to produce strong fluorescence peak located at 423 nm. This peak red-shifts to 489 nm, which is induced by the strengthening of intermolecular hydrogen bond (HB) between PTI and water molecules and attributed to the experimentally observed fluorescence emission at 503 nm. This result is dramatically different from previous reports that the experimental fluorescence corresponds to the proton transferred enol form of PTI. To illustrate this confusion, the calculated fluorescence peak of PTI-Enol is located at 689 nm, which is much larger than that of experimental result. This result excludes the occurrence of excited state intramolecular proton transfer (ESIPT). It is concluded that intermolecular HBs hinders the formation of intramolecular HB and the ESIPT of the keto form of PTI. This conclusion confirms that experimental Stokes shift of 113 nm is mainly caused by the intermolecular hydrogen bonding rather than by ESIPT process. This work proposes a reasonable explanation for the detection mechanism of CORM3-green and experimental fluorescence phenomenon. [ABSTRACT FROM AUTHOR]