Aromaticity of Bare Iridium Trimers and Ir3M0/+ and Ir3M2+/3+\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\rm{Ir}_3M_2^{+/3+}$$\end{document} (M = Li, Na, K, and Be, Ca) Bimetallic Clusters

被引：0
作者：
Q. Jin
B. Jin
Z.-H. Zhang
X.-N. He
机构：
[1] Beijing Institute of Petrochemical Technology,National Demonstration Center for Experimental Chemistry and Chemical Engineering Education, School of Chemical Engineering
[2] Shenyang University of Chemical Technology,School of Environment and Biology Engineering
来源：
Journal of Structural Chemistry | 2018年 / 59卷 / 5期
关键词：
iridium trimers; aromaticity; DFT calculation;
D O I：
10.1134/S0022476618050049
中图分类号：
学科分类号：
摘要：
The structural stabilities, bonding nature, electronic properties, and aromaticity of bare iridium trimers Ir3+/−\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\rm{Ir}_3^{+/-}$$\end{document} with different geometries and spin multiplicities are studied at the DFT/B3LYP level of theory. The ground state of the Ir3+\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\rm{Ir}_3^{+}$$\end{document} cation is found to be the 3A2 (C2v) triplet state and the ground state of the Ir3−\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\rm{Ir}_3^{-}$$\end{document} anion the 5A2 (C2v) quintet state. A detailed molecular orbital (MO) analysis indicates that the ground-state Ir3+\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\rm{Ir}_3^{+}$$\end{document} ion (C2v, 3A2) possesses double (σ and partial δ) aromaticity as well as the ground-state Ir3−\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\rm{Ir}_3^{-}$$\end{document} ion (C2v, 5A2). The multiple d-orbital aromaticity is responsible for the totally delocalized three-center metal-metal bond of the triangular Ir3 framework. Ir3−\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\rm{Ir}_3^{-}$$\end{document} (C2v, 1A1) structure motif is perfectly preserved in pyramidal Ir3M0/+ (Cs, 1A′) and bipyramidal Ir3M2+/3+\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\rm{Ir}_3M_2^{+/3+}$$\end{document} (C2v, 1A1) (M = Li, Na, K and Be, Ca) bimetallic clusters which also possess the corresponding d-orbital aromatic characters.
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页码：1032 / 1043
页数：11
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