title: Fluoride anion sensing mechanism of 2-ureido-4[1H]-pyrimidinone quadruple hydrogen-bonded supramolecular assembly: photoinduced electron transfer and partial configuration change.
abstract: The fluoride anion sensing mechanism of 6-methyl-5-(9-methylene-anthracene)-(2-butylureido-4[1H]-pyrimidinone) (AnUP) has been investigated using the DFT/TDDFT method. The theoretical results indicate that the proton of the N3-H3 group in pyrimidine moiety is captured by the added fluoride anion and then deprotonated. The calculated vertical excitation energies of AnUP-dimer and its deprotonated form agree well with the experimental results. The molecular orbital analysis demonstrates that the first excited state (S1) of AnUP-dimer is a local excited state with a π-π* transition, whereas for the deprotonated form, S1 is a completely charge-separation state and is responsible for the photoinduced electron transfer (PET) process. The PET process from anthracene to the pyrimidine moiety leads to the fluorescence quenching.
authors.affiliation: State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences Dalian 116023, People's Republic of China.
authors.forename: Jun-Sheng
authors.initials: JS
authors.lastname: Chen
authors.forename: Pan-Wang
authors.initials: PW
authors.lastname: Zhou
authors.forename: Guang-Yue
authors.initials: GY
authors.lastname: Li
authors.forename: Tian-Shu
authors.initials: TS
authors.lastname: Chu
authors.forename: Guo-Zhong
authors.initials: GZ
authors.lastname: He
mesh_terms: D000838:Anions / Q000737:chemistry; D019281:Dimerization; D004579:Electron Transport; D005459:Fluorides / Q000737:chemistry*; D006860:Hydrogen Bonding; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D011522:Protons; D011744:Pyrimidinones / Q000737:chemistry*; D011789:Quantum Theory; D013056:Spectrophotometry, Ultraviolet; D013816:Thermodynamics
chemical_list: C109276:2-ureido-4-pyrimidone; D000838:Anions; D011522:Protons; D011744:Pyrimidinones; D005459:Fluorides