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| A Tetradecanuclear Polyoxofluorovanadate Cluster Compound with 1-Methylimidazole Possessing Ring-like[V10O20] Ladder Core and Unusual Electronic Configuration: Synthesis, Structure and Theoretical Calculation |
| Author Name | Affiliation | E-mail | | TONG Yi-Ping | School of Chemistry and Materials Engineering, Huizhou University, Huizhou, Guangdong 516007, China
Center of Green Chemical Engineering and Functional Materials of Guangdong Provincial Universities, Huizhou, Guangdong 516007, China | | | ZHENG Xiao-Dan | School of Chemistry and Materials Engineering, Huizhou University, Huizhou, Guangdong 516007, China
Center of Green Chemical Engineering and Functional Materials of Guangdong Provincial Universities, Huizhou, Guangdong 516007, China | | | LI Jia-Jia | School of Chemistry and Materials Engineering, Huizhou University, Huizhou, Guangdong 516007, China
Center of Green Chemical Engineering and Functional Materials of Guangdong Provincial Universities, Huizhou, Guangdong 516007, China | | | LIN Yan-Wen | School of Life Science, Huizhou University, Huizhou, Guangdong 516007, China | | | LUO Guo-Tian | College of Chemistry and Life Science, Gannan Normal University, Ganzhou, Jiangxi 341000, China | typ2469@163.com |
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| Abstract: A rare tetradecanuclear polyoxofluorovanadate cluster with 1-methylimidazole (L), containing mixed-valence[V14O36F2L2]6- anion, was synthesized and characterized crystallographically. The anion is composed of a special 0D cluster-like skeleton frame, i.e. the ring-shaped[V10O20] ladder, two grafted VO5F and VO3L fragments around the ladder. The density functional theory (DFT) and bond valence sum calculations indicate that the V ion in two grafted VO5F fragments are +4 oxidation state, while other V ions are +5 oxidation state. The frontier orbital analysis shows that the[V14O36F2L2]6- anion, should be chemically active in d orbital of grafted VO5F fragments, while its 2e oxidation species, the[V14O36F2L2]4- anion should be chemically active in the terminal V=O (d-p) π orbital of grafted VO3L fragments. The 2e introduction from[V14O36F2L2]4- to[V14O36F2L2]6- anion leads to the increasing structural stability of the[V10O20] ladder, and at the same time the increasing chemical activity of the grafted VO5F and VO3L fragments, together with a great decrease of energy gap from 1.59 to 0.53 eV. |
| Keywords: polyoxofluorovanadate DFT calculation ladder-like energy gap molecular fragment 1-methylimidazole |
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| TONG Yi-Ping,ZHENG Xiao-Dan,LI Jia-Jia,LIN Yan-Wen,LUO Guo-Tian.A Tetradecanuclear Polyoxofluorovanadate Cluster Compound with 1-Methylimidazole Possessing Ring-like[V10O20] Ladder Core and Unusual Electronic Configuration: Synthesis, Structure and Theoretical Calculation[J].Chinese Journal of Inorganic Chemistry,2019,35(6):1093-1100. |
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