一种新的二帽Keggin多金属氧酸盐的合成、表征及磁性

doi:10.11944/j.issn.1000-0518.2015.09.150027

摘要/Abstract

摘要：

在水热条件下合成了一种新的二帽二支撑的Keggin型钼钒多金属氧酸盐[Cu(2,2'-bpy)₃]{[Cu(2,2'-bpy)₂]₂HP^ⅤMo8VIV6IVO₄₂]}·2H₂O(1,bpy=联吡啶),利用元素分析、红外光谱、X射线光电子能谱,粉末和X射线单晶衍射等分析技术对化合物的晶体结构进行了表征。结果表明,该化合物属于单斜晶系,C2/c空间群,a=2.8734(3) nm,b=1.47333(12) nm,c=2.31023(16) nm,β=112.509(5)°,V=9.0351(12) nm³,Z=1,R₁=0.0489,wR₂=0.1286。化合物的阴离子是二帽α-Keggin结构P/Mo/V多金属氧簇,通过簇阴离子两个钒帽上的端氧分别支撑两个铜过渡金属配合物,化合物簇阴离子,水分子和2,2'-联吡啶分子之间通过π-π和氢键作用形成了三维超分子结构。

关键词: 水热合成, Keggin结构, 超分子, 磁性

Abstract:

A new bicapped Keggin molybdenum-vanadium polyoxometalate [Cu(2,2'-bpy)₃]{[Cu(2,2'-bpy)₂]₂HP^ⅤMo8VIV6IVO₄₂}}·2H₂O 1(bpy=bipyridien) was prepared under hydrothermal conditions, and characterized by elemental analysis, IR, X-ray photoelectron spectroscopy, powder and single crystal X-ray diffraction analysis. The compound 1 crystallized in a monoclinic system, with a C2/c space group:a=2.8734(3) nm, b=1.47333(12) nm, c=2.31023(16) nm, β=112.509(5)°, V=9.0351(12) nm³, Z=1, R₁=0.0489, wR₂=0.1286. The polyoxoanion of compound 1 is a bi-capped P/Mo/V Keggin cluster supporting two copper complexes fragment through the oxygen of capping V atoms of polyoxoanion. Compound 1 exhibits an extended three-dimensional supramolecular network via hydrogen-bonding and π-π stacking interactions between polyoxoanion, water molecules and 2,2'-bpy molecules.

Key words: hydrothermal synthesis, Keggin structure, supramolecular, magnetic properties

张春峰,孙英华. 一种新的二帽Keggin多金属氧酸盐的合成、表征及磁性[J]. 应用化学, 2015, 32(9): 1055-1060.

ZHANG Chunfeng,SUN Yinghua. Hydrothermal Synthesis, Structure Characterization and Magnetism Property of a New Bi-capped Keggin Polyoxometalate[J]. Chinese Journal of Applied Chemistry, 2015, 32(9): 1055-1060.

参考文献

[1]	Hagrman P J,Hagrman D,Zubieta J. Organic-Inorganic Hybrid Materials: From “Simple” Coordination Polymers to Organodiamine-Templated Molybdenum Oxides[J]. Angew Chem Int Ed,1999,38(18):2638-2684.
[2]	Müller A,Krickemeyer E,Bögge H,et al.“Nanoobjects” by Self-Assembly Concomitant with Modifications Under Alterable Boundary Conditions:Incorporation of Paramagnetic Metal Centers (Cu2+) in Ring-Shaped Molybdenum-Oxide Based Clusters[J]. Angew Chem Int Ed,2001,40(21):4034-4037.
[3]	Müller A,Kögerler P,Dress A W M. Giant Metal-oxide-based Spheres and Their Topology:From Pentagonal Building Blocks to Keplerates and Unusual Spin Systems[J]. Coord Chem Rev,2001,222(1):193-218.
[4]	Müller A,Roy S. En Route From the Mystery of Molybdenum Blue via Related Manipulatable Building Blocks to Aspects of Materials Science[J]. Coord Chem Rev,2003,245(1/2):153-166.
[5]	WANG Enbo,HU Changwen,XU Lin,et al.Polyoxometalate Chemistry Introduction[M]. Beijing:Chemical Industry Press,1998:14-47(in Chinese). 王恩波,胡长文,许林,等. 多酸化学导论[M]. 北京:化学工业出版社,1998:14-47.
[6]	Hagrman P J,Zubieta J. Solid-State Coordination Chemistry of Metal Oxides:Hydrothermal Synthesis and Structural Characterization of o-Phenanthroline-Ligated Copper- and Zinc-Molybdenum Oxides[J]. Inorg Chem,1999,38(20):4480-4485.
[7]	Xu J Q,Wang R Z,Yang G Y,et al.Metal oxo Cluster-supported Transition Metal Complexes:Hydrothermal Synthesis and Characterization of [{M(phen)2}2(Mo8O26)](M=Ni or Co)[J]. Chem Commun,1999,(11):983-984.
[8]	Burkholder E,Golub V,O'Connor C J,et al. Solid State Coordination Chemistry:One-, Two-, and Three-Dimensional Materials Constructed from Molybdophosphonate Subunits Linked Through Binuclear Copper Tetra-2-Pyridylpyrazine Groups[J]. Inorg Chem,2003,42(21):6729-6740.
[9]	Han Z G,Chang X Q,Yan J S,et al.An Unusual Metallic Oxygen Cluster Consisting of a {AlMo12O40(MoO2)}[J]. Inorg Chem,2014,53(2):670-672.
[10]	Brown I D,Altermatt D. Bond-valence Parameters Obtained from a Systematic Analysis of the Inorganic Crystal Structure Database[J]. Acta Crystallogr,Sect B:Struct Sci,1985,41(4):244-247.
[11]	Li Y G,Wang E B,Wang S T,et al.A Highly Reduced Polyoxoanion with Phosphorus-cented Alternate Layers of Mo/V Oxides, [PMoV2MoVI6VIV4O40(VIVO)2]9-[J]. J Mol Struct,2002,611(1/2/3):185-191.
[12]	Xiao L N,Wang Y,Chen Y,et al.A Novel Polyoxometalate Tri-supported Mixed-valent Transition Metal Coordination Complex[J]. Inorg Chem Comm,2010,13(10):1217-1220.
[13]	Lisnard L,Dolbecq A,Mialane P,et al.Molecular and Multidimensional Polyoxotungstates Functionalized by {Cu(bpy)}2+ Groups[J]. Dalton Trans,2005,(24):3913-3920.

[1]	杨倩, 张杨, 赖明阳, 郭琳, 郏建波. 不同热解温度下制备的磁性生物炭对罗丹明B的吸附性能[J]. 应用化学, 2023, 40(2): 288-298.
[2]	王凯, 杨海宽, 刘慧兰, 路嘉敏, 张晨. 基于豆甾醇衍生物的超分子凝胶的合成与性能[J]. 应用化学, 2022, 39(9): 1453-1463.
[3]	刘也, 郭少波, 梁艳莉, 葛红光, 马剑琪, 刘智峰, 刘波. 核壳型纳米复合材料CuFe₂O₄@NH₂@Pt的制备及催化性能[J]. 应用化学, 2022, 39(8): 1237-1245.
[4]	曹从军, 马含笑, 侯成敏, 丁小健, 管飙. 乙基纤维素磁性复合材料对溶液中铜离子的吸附性能[J]. 应用化学, 2022, 39(6): 969-979.
[5]	杜慧, 姚晨阳, 彭皓, 姜波, 李顺祥, 姚俊烈, 郑方, 杨方, 吴爱国. 过渡金属掺杂磁性纳米粒子在生物医学领域中的研究进展[J]. 应用化学, 2022, 39(3): 391-406.
[6]	赵常利, 秦明高, 窦晓秋, 冯传良. 纳米颗粒增强的手性超分子水凝胶成骨性能[J]. 应用化学, 2022, 39(1): 177-187.
[7]	王后臣, 周利, 刘洋, 陈明月, 石铁生. 超分子聚集体构筑单元的分子设计及其自组装研究进展[J]. 应用化学, 2021, 38(6): 615-621.
[8]	邓媛, 范遥见, 陶磊, 骆支旺, 谢鹤楼. 含有偶氮苯液晶纳米粒子的合成及其超分子结构和光控取向行为[J]. 应用化学, 2021, 38(10): 1353-1361.
[9]	肖海梅, 蔡蕾, 张朝晖, 陈珊, 周姝, 符金利. 磁性氧化石墨烯/MIL-101(Cr)表面金属离子印迹聚合物制备及其对Cu(Ⅱ)和Pb(Ⅱ)选择性吸附[J]. 应用化学, 2020, 37(9): 1076-1086.
[10]	张转芳, 郑建华, 辛建娇, 赵楠, 陈洁, 许芮. Keggin型多酸基晶态材料的合成及催化性能[J]. 应用化学, 2020, 37(4): 481-488.
[11]	王秋实, 贺军辉. 磁性硫化铜复合纳米材料的合成及其对水中汞离子的特异性吸附[J]. 应用化学, 2020, 37(11): 1316-1323.
[12]	弓韬, 黄昱, 郭国英, 苏丹, 梁文婷, 董川. 线性麦芽糊精聚合物功能化Fe₃O₄纳米复合物药物载体的合成和应用[J]. 应用化学, 2019, 36(2): 161-169.
[13]	陈红云,杨方红,李宇鹏,何佳玉,车梦琴,王美晨,程传杰. 水溶性Fe₃O₄磁性纳米催化剂的合成及应用[J]. 应用化学, 2019, 36(2): 188-194.
[14]	王琦, 仝玉章, 贾晓普, 杨春, 王庆伦, 廖代正. 基于N,N'-双(3-吡啶基)-对苯二甲酰胺和1,3,5-苯三甲酸的二维Co(Ⅱ)金属有机骨架的合成、结构和磁性[J]. 应用化学, 2019, 36(12): 1397-1405.
[15]	李文进, 姚威龙, 徐嘉鑫, 蒋琪英, 邓洪权. Ho³⁺掺杂铁酸铋的制备及光催化性[J]. 应用化学, 2019, 36(1): 91-96.