Quantum chemical study of the photolysis mechanisms of sulfachloropyridazine and the influence of selected divalent metal ions.
Sulfonamides have been found in aquatic environments. Degradation of sulfachloropyridazine (SCP) mainly proceeds through direct and indirect photolysis in the aquatic environment. However, the mechanisms underlying the triplet photolysis of SCP and the influence of metal ions on the photolysis mechanism have not yet been fully explained. In this study, we elucidated the triplet photolysis mechanisms of SCP and the effects of three selected metal ions (Zn(2+), Ca(2+), and Cu(2+)) on the SCP photolysis mechanisms using quantum chemical calculation. Optimization of molecular structures and reaction pathways analysis of SCP were carried out at the B3LYP/6-31+G(d,p) level of theory. Two minimum energy pathways were investigated in the triplet photolysis of SCP. In Step 2 of Path-I, the photolysis product of SCP is a sulfur dioxide extrusion product, (4-(3-chloro-6-iminopyridazine-1(6H)-yl)aniline). The estimated activation energies of Step 2 and Step 3 of Path-I were much higher than in Path-II. Therefore, Path-II was found as the lowest energy pathway to obtain the SCP photoproducts, and Step 2 of Path-II was confirmed as the rate-determining step (RDS) in the photolysis mechanism of SCP. For the RDS of Path-II, computations with the three metal ions complexes (IM1-Cu(2+), IM1-Ca(2+), and IM1-Zn(2+)) show that the metal ions Cu(2+) and Ca(2+) promote triplet-sensitized photolysis of SCP by reducing the activation energy of RDS of Path-II, whereas Zn(2+) showed an inhibitory effect in photolysis of SCP by increasing the activation energy.
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, China.
Shaheen
S
Shah
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, China.
Heming
H
Zhang
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, China.
Xuedan
X
Song
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, China. Electronic address: haoce@dlut.edu.cn.
Ce
C
Hao
D002413:Cations, Divalent / Q000737:chemistry; D019216:Metals, Heavy / Q000737:chemistry*; D008958:Models, Molecular; D008962:Models, Theoretical; D015394:Molecular Structure; D010782:Photolysis; D011789:Quantum Theory; D013410:Sulfachlorpyridazine / Q000737:chemistry* / Q000528:radiation effects; D014874:Water Pollutants, Chemical / Q000737:chemistry* / Q000528:radiation effects
D002413:Cations, Divalent; D019216:Metals, Heavy; D014874:Water Pollutants, Chemical; D013410:Sulfachlorpyridazine
Activation energy; DFT; Metal ions; Photolysis mechanism; Sulfachloropyridazine