caa a22 4500 605512698 CHVBK 20210128100656.0 cr unu---uuuuu 210128e20150401xx s 000 0 eng 10.1007/s00894-015-2619-z doi (NATIONALLICENCE)springer-10.1007/s00894-015-2619-z Electronic effects of the substituent on the dioxygen-activating abilities of substituted iron tetraphenylporphyrins: a theoretical study [Elektronische Daten] [Haiyan Fu, Meijuan Cao, Yuanbin She, Zhicheng Sun, Yanmin Yu] A density functional theoretical (DFT) method was applied to understand the effects of the substituent on dioxygen activation by a series of substituted iron tetraphenylporphyrins [FeT(o/p-R)PP (o = ortho-substituted, p = para-substituted; R = −H, −Cl, −NO2, −CH3, −OCH3)]. The ground states (GS) of the dioxygen adducts of the substituted iron tetraphenylporphyrins [FeT(o/p-R)PPO2] were determined at the B3LYP/6-31G(d) level without any symmetry constraints. Binding energy calculations indicated that the presence of electron-withdrawing substituents at the para position favors O2 binding. Calculations of the O-O bond length of the adsorbed dioxygen revealed that the influence of the p-substituent on the activation of dioxygen decreases in the order p-CH3 > p-Cl > p-OCH3 > −H > p-NO2, while the influence of the o-substituent decreases in the order o-NO2 > o-CH3 > o-Cl > o-OCH3 > −H. The low-lying excited states (LLES) of the FeT(o/p-R)PPO2 adducts suggest that the ability to activate dioxygen decreases in the order o-CH3 > o-OCH3 = −H > o-NO2 > o-Cl for o-substituents and p-CH3 > p-Cl > −H > p-NO2 > p-OCH3 for p-substituents. NBO charge population analysis and spin density analysis showed that substitution caused more β-electrons to be transferred from the iron tetraphenylporphyrin to the dioxygen, which enhanced dioxygen activation. Spin density analysis confirmed that the β-electron population at the adsorbed dioxygen is an accurate indicator of the degree of dioxygen activation. The trend observed in porphyrin catalytic activity as the substituent on the dioxygen adduct was varied is consistent with the trend in the binding energy. It is clear that substituents at the ortho and para positions in these dioxygen adducts play different roles in dioxygen activation. Graphical Abstract The electronic effects of the substituents (-Cl, -NO2, -CH3, -OCH3) on the dioxygen-activating abilities of substituted iron tetraphenylporphyrins were studied by density functional theoretical method. The results indicated that substituents at the para- and otho- position have a significant effect on the O2 binding energy Springer-Verlag Berlin Heidelberg, 2015 Iron tetraphenylporphyrins nationallicence Substituent effect nationallicence DFT nationallicence Dioxygen adducts nationallicence Dioxygen activation nationallicence Fu Haiyan College of Pharmacy, South-Central University for Nationalities, 430074, Wuhan, China aut Cao Meijuan Beijing Engineering Research Center of Printed Electronics, School of Printing and Packaging Engineering, Beijing Institute of Graphic Communication, 102600, Beijing, China aut She Yuanbin State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, College of Chemical Engineering, Zhejiang University of Technology, 310014, Hangzhou, China aut Sun Zhicheng Beijing Engineering Research Center of Printed Electronics, School of Printing and Packaging Engineering, Beijing Institute of Graphic Communication, 102600, Beijing, China aut Yu Yanmin Institute of Green Chemistry and Fine Chemicals, College of Environmental & Energy Engineering, Beijing University of Technology, 100124, Beijing, China aut Journal of Molecular Modeling Springer Berlin Heidelberg 21/4(2015-04-01), 1-10 1610-2940 21:4<1 2015 21 894 https://doi.org/10.1007/s00894-015-2619-z text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00894-015-2619-z text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Fu Haiyan College of Pharmacy, South-Central University for Nationalities, 430074, Wuhan, China aut NATIONALLICENCE 700 1- Cao Meijuan Beijing Engineering Research Center of Printed Electronics, School of Printing and Packaging Engineering, Beijing Institute of Graphic Communication, 102600, Beijing, China aut NATIONALLICENCE 700 1- She Yuanbin State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, College of Chemical Engineering, Zhejiang University of Technology, 310014, Hangzhou, China aut NATIONALLICENCE 700 1- Sun Zhicheng Beijing Engineering Research Center of Printed Electronics, School of Printing and Packaging Engineering, Beijing Institute of Graphic Communication, 102600, Beijing, China aut NATIONALLICENCE 700 1- Yu Yanmin Institute of Green Chemistry and Fine Chemicals, College of Environmental & Energy Engineering, Beijing University of Technology, 100124, Beijing, China aut NATIONALLICENCE 773 0- Journal of Molecular Modeling Springer Berlin Heidelberg 21/4(2015-04-01), 1-10 1610-2940 21:4<1 2015 21 894