Due to the fulfilled s
Chinese Journal of Chemical Physics, Volume. 33, Issue 5, 578(2020)
Designer Mg?Mg and Zn?Zn Single Bonds Facilitated by Double Aromaticity in the M2B7- (M=Mg, Zn) Clusters†
The simple homodinuclear M$ - $M single bonds for group II and XII elements are difficult to obtain as a result of the fulfilled s$ ^2 $ electronic configurations, consequently, a dicationic prototype is often utilized to design the M$ ^+ $$ - $M$ ^+ $ single bond. Existing studies generally use sterically bulky organic ligands L$ ^- $ to synthesize the compounds in the L$ ^- $$ - $M$ ^+ $$ - $M$ ^+ $$ - $L$ ^- $ manner. However, here we report the design of Mg$ - $Mg and Zn$ - $Zn single bonds in two ligandless clusters, Mg$ _2 $B$ _7 $$ ^- $ and Zn$ _2 $B$ _7 $$ ^- $, using density functional theory methods. The global minima of both of the clusters are in the form of M$ _2 $$ ^{2+} $(B$ _7 $$ ^{3-} $), where the M$ - $M single bonds are positioned above a quasi-planar hexagonal B$ _7 $ moiety. Chemical bonding analyses further confirm the existence of Mg$ - $Mg and Zn$ - $Zn single bonds in these clusters, which are driven by the unusually stable B$ _7 $$ ^{3-} $ moiety that is both $ \sigma $ and $ \pi $ aromatic. Vertical detachment energies of Mg$ _2 $B$ _7 $$ ^- $ and Zn$ _2 $B$ _7 $$ ^- $ are calculated to be 2.79 eV and 2.94 eV, respectively, for the future comparisons with experimental data.
Ⅰ INTRODUCTION
Due to the fulfilled s
Figure 1.Correlation diagram for the valence molecular orbitals showing the bond orders of (a) M
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For the case of Mg
In the current study, we aim to design ligandless Mg-Mg and Zn-Zn single bonds in the form of cluster anions with density functional theory (DFT) methods. Anionic clusters, instead of neutral or cationic clusters, are calculated on purpose because we anticipate potential comparisons with future anion photoelectron spectroscopic studies, which have been proven to be a great experimental tool to interrogate the nature of chemical bonds in gas-phase clusters [22-32]. In the wish of constructing a M
Ⅱ THEORETICAL METHODS
Unbiased global geometric searches using the coalescence kick (CK) program [35] were performed to locate the global minima (GM) of the M
Figure 2.Six lowest isomers and their relative energies of the Mg
Figure 3.AdNDP analyses of the chemical bonding in the GM of the Mg
Figure 4.Six lowest isomers and their relative energies of the Zn
Ⅲ RESULTS AND DISCUSSION
The six lowest energy isomers of Mg
To further investigate the bonding situation, we have also performed the AdNDP analysis of the GM of the Mg
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The six lowest energy isomers of Zn
Figure 5.AdNDP analyses of the chemical bonding in the GM of the Zn
Ⅳ CONCLUSION
To conclude, here we have reported a DFT study of the designer M
Ⅴ ACKNOWLEDGMENTS
This work was supported by the National Key R & D Program of China (No.2018YFE0115000) and the Natural Science Foundation of Tianjin City (No.19JCYBJC19600).
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Wei Wang, Jie Wang, Chu Gong, Chaonan Mu, Dongmei Zhang, Xinxing Zhang. Designer Mg?Mg and Zn?Zn Single Bonds Facilitated by Double Aromaticity in the M2B7- (M=Mg, Zn) Clusters†[J]. Chinese Journal of Chemical Physics, 2020, 33(5): 578
Received: Apr. 27, 2020
Accepted: May. 25, 2020
Published Online: Apr. 21, 2021
The Author Email: Xinxing Zhang (zhangxx@nankai.edu.cn)