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Huan‐Cheng Hu Han‐Shi Hu Bin Zhao Ping Cui Peng Cheng Jun Li 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2015,127(40):11847-11851
MOFs with both multicentered metal–metal bonds and low‐oxidation‐state (LOS) metal ions have been underexplored hitherto. Here we report the first cubic [MnI8] cluster‐based MOF ( 1 ) with multicentered MnI MnI bonds and +1 oxidation state of manganese (MnI or Mn(I)), as is supported by single‐crystal structure determination, XPS analyses, and quantum chemical studies. Compound 1 possesses the shortest MnI MnI bond of 2.372 Å. Theoretical studies with density functional theory (DFT) reveal extensive electron delocalization over the [MnI8] cube. The 48 electrons in the [MnI8] cube fully occupy half of the 3d‐based and the lowest 4s‐based bonding orbitals, with six electrons lying at the nonbonding 3d‐orbitals. This bonding feature renders so‐called cubic aromaticity. Magnetic properties measurements show that 1 is an antiferromagnet. This work is expected to inspire further investigation of cubic metal–metal bonding, MOF materials with LOS metals, and metalloaromatic theory. 相似文献
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