Sensing Mechanism for Biothiols Chemosensor DCO: Roles of Excited-State Hydrogen-Bonding and Intramolecular Charge Transfer

Chen, JunshengLund University,Lunds universitet,Kemisk fysik,Enheten för fysikalisk och teoretisk kemi,Kemiska institutionen,Institutioner vid LTH,Lunds Tekniska Högskola,Chemical Physics,Physical and theoretical chemistry,Department of Chemistry,Departments at LTH,Faculty of Engineering, LTH (author)

The biothiols sensing mechanism of (E)-7-(diethylamino)-3-(2-nitrovinyl)-2H-chromen-2-one (DCO) has been investigated using the density functional theory (DFT) and time-dependent DFT methods. The theoretical results indicate that the excited-state intermolecular hydrogen bonding (H-B) plays an important role for the biothiols sensing mechanism of the fluorescence sensor DCO. Multiple H-B interaction sites exist in DCO and in its Michael addition product DCOT, which then induce the formation of the H-B complexes with water molecules, DCOH2 and DCOTH4. In the first excited state, the intermolecular H-Bs between water molecule and DCO in DCOH2 are cooperatively and generally strengthened and thus induced the weak fluorescence emission of DCO, while the cooperative H-Bs between water molecule and DCOT in DCOTH4 are overall weakened and thus responsible for the enhanced fluorescence emission of DCOT. Moreover, the theoretical results suggest that the blue shift of the UV-Vis absorption spectrum of DCOT can be attributed to the relatively weak excited-state intramolecular charge transfer in DCOT compared to DCO.

In:The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory: American Chemical Society (ACS)118:39, s. 8986-89951520-5215
In:The Journal of Physical Chemistry A: American Chemical Society (ACS)118:39, s. 8986-89951089-5639

By the author/editor: Chen, Junsheng; Yuan, Ming-Hu; Wang, Jia-Pei; Yang, Yang; Chu, Tian-Shu

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