Theoretical study on the luminescent and reaction mechanism of dansyl‐based fluorescence probe for detecting hydrogen sulfide

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Abstract
The photophysical and photochemical properties of the sulfonyl azide‐based fluorescent probe DNS–Az and its reduction product DNS by hydrogen sulfide (H2S) have been investigated theoretically. The calculated results indicated the first excited states of DNS–Az was dark state (oscillator strength less than 0.03) and DNS was bright state (oscillator strength more than 0.1), which determined the predicted radiative rate kr of DNS–Az was much smaller than that of DNS, meanwhile, due to more larger reorganization energy of DNS–Az, its predicted internal conversion rate kic was four times larger than that of DNS; moreover, owing to the effect of heavy atom from sulfur atom in DNS–Az, its predicted intersystem crossing rate kisc was seven times larger than that of DNS, thus the calculated fluorescence quantum yield of DNS–Az was only 2.16% and that of DNS was more than 77.2%, the above factors is the basis for DNS–Az molecule to function as a fluorescent probe. Regarding both DNS‐Az and DNS molecules, their maximum Huang‐Rhys factors, which are less than unity, signify the reliability of 0–0 transitions between their S0 and S1 electronic states. In addition, for DNS, our simulated emission peak of the 0–0 transition is 515 nm, a value that exhibits enhanced accuracy and coherence when compared to the experimental datum of 528 nm. The reaction mechanism of DNS‐Az generating DNS by H2S has been investigated too, according to the potential energy profile, we found that the fluorescent probe firstly protonated, then this organic ion broke down into DNS with the aid of a proton.

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