一个含1-甲基咪唑的环状梯型核[V10O20]及特别的电子构型的十核钒氧簇合物的合成、结构及理论计算（英文）  

A Tetradecanuclear Polyoxofluorovanadate Cluster Compound with1-Methylimidazole Possessing Ring-like [V10O20] Ladder Core and Unusual Electronic Configuration: Synthesis, Structure and Theoretical Calculation

作　　者：童义平 郑晓丹 李佳佳 林燕文 罗国添[4] TONG Yi-Ping;ZHENG Xiao-Dan;LI Jia-Jia;LIN Yan-Wen;LUO Guo-Tian(School of Chemistry and Materials Engineering,Huizhou University,Huizhou,Guangdong 516007,China;Center of Green Chemical Engineering and Functional Materials of GuangdongProvincial Universities,Huizhou,Guangdong 516007,China;School of Life Science,Huizhou University,Huizhou,Guangdong 516007,China;College of Chemistry and Life Science,Gannan Normal University,Ganzhou,Jiangxi 341000,China)

机构地区：[1]惠州学院化学与材料工程学院,惠州516007 [2]广东高校绿色化工与功能材料工程技术开发中心,惠州516007 [3]惠州学院生命科学学院,惠州516007 [4]赣南师范大学化学化工,赣州341000

出　　处：《无机化学学报》2019年第6期1093-1100,共8页Chinese Journal of Inorganic Chemistry

基　　金：广东省普通高校创新团队项目无机固体功能材料研究团队(No.2015KCXTD030);国家自然科学基金(No.21271080);广东高校绿色化工与功能材料工程技术开发中心建设项目;惠州市科技计划项目(No.2012B020004006)资助~~

摘　　要：合成并表征了一个稀少的含1-甲基咪唑(L)及混合价的[V14O36F2L2]6-阴离子化合物的晶体结构。该阴离子是由一个环状的[V10O20]梯和2对架于梯上的VO5F及VO3L碎片组成。DFT及键价计算表明架着的VO5F碎片中V是+4价,其余V均为+5价。前线分子轨道分析表明:[V14O36F2L2]^6-阴离子架着的VO5F碎片中,V的d轨道是化学上活性的;而其2e氧化型[V14O36F2L2]^4-阴离子的VO3L碎片中,端基V=O(d-p)π轨道是化学上活性的。从[V14O36F2L2]^4-变成[V14O36F2L2]6-阴离子,2e的引入,导致了[V10O20]梯更加稳固,但架于其上的VO5F及VO3L碎片却越来越活泼(不稳定),并且能隙大幅降低(从1.59eV变为0.53eV)。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.CCDC: 761054.

关 键 词：聚钒氧酸盐 DFT计算 梯型 能隙 分子碎片 1-甲基咪唑 

分 类 号：O614.511[理学—无机化学]