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.
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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: Zhang Xinxing (zhangxx@nankai.edu.cn)