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Evans–Showell-Type Polyoxometalates Constructing High-Dimensional Inorganic–Organic Hybrid Compounds with Copper–Organic Coordination Complexes: Synthesis and Oxidation Catalysis
Inorganic Chemistry ( IF 4.6 ) Pub Date : 2017-09-18 00:00:00 , DOI: 10.1021/acs.inorgchem.7b01564
Haiyan An 1 , Yujiao Hou 1 , Lin Wang 1 , Yumeng Zhang 1 , Wei Yang 1 , ShenZhen Chang 1
Affiliation  

Four new hybrid architectures containing a [Co2Mo10H4O38]6– polyoxoanion, (en)[Cu3(ptz)4(H2O)4][Co2Mo10H4O38]·24H2O (1), (Hbim)2[{Cu(bim)2(H2O)2}2{Co2Mo10H4O38}]·5H2O (2), H2[Cu(dpdo)3(H2O)4][{Cu2(dpdo)3(H2O)4(CH3CN)}2{Co2Mo10H4O38}2]·9H2O (3), and (H2bpp)4[{Cu(H2O)2}{NaCo2Mo10H4O38}2]·10H2O (4), where ptz = 5-(4-pyridyl)-1H-tetrazole, en = ethylenediamine, bim = benzimidazole, dpdo = 4,4′-bipyridine-N,N′-dioxide, and bpp = 1,3-bis(4-pyridyl)propane, have been prepared and characterized through elemental analysis, thermogravimetric analysis, IR spectroscopy, and powder and single-crystal X-ray diffraction. Compound 1 shows a 3D host–guest framework composed of 3D Cu-ptz as the host and Evans–Showell-type polyoxoanion [Co2Mo10H4O38]6– as the guest. Compound 2 is constructed from [Co2Mo10H4O38]6– polyoxoanions and Cu-bim coordination complexes to form a 2D covalent layer. Compound 3 also exhibits a 2D hybrid network based on [Co2Mo10H4O38]6– polyoxoanions linked by Cu-dpdo coordination groups. Compound 4 is a 1D double-chain structure composed of [Co2Mo10H4O38]6– polyoxoanions joined together by Na+ and Cu2+ cations. As far as we know, compound 1 is the first host–guest compound with an Evans–Showell-type polyoxometalate as the guest, and compounds 2 and 3 are the first 2D inorganic–organic hybrid architectures constructed from Evans–Showell-type polyoxometalates. Compounds 14 are redox catalysts that heterogeneously prompt sulfide and alcohol oxidation with excellent efficiency.

中文翻译:

Evans-Showell型多金属氧酸盐与铜-有机配位化合物一起构建高维无机-有机杂化化合物:合成和氧化催化

包含[Co 2 Mo 10 H 4 O 38 ] 6–聚氧阴离子,(en)[Cu 3(ptz)4(H 2 O)4 ] [Co 2 Mo 10 H 4 O 38 ]·24H 2的四种新型混合体系结构O(1),(Hbim)2 [{Cu(bim)2(H 2 O)2 } 2 {Co 2 Mo 10 H 4 O 38 }]·5H 2 O(2),H 2 [Cu(dpdo)3(H 2 O)4 ] [{Cu 2(dpdo)3(H 2 O)4(CH 3 CN)} 2 {Co 2 Mo 10 H 4 O 38 } 2 ] ·9H 2 O(3)和(H 2 bpp)4 [{Cu(H 2 O)2 } {NaCo 2 Mo 10 H 4 O 38 } 2 ]·10H 2 O(4),其中ptz = 5-(4-吡啶基)-1 H-四唑,en =乙二胺,bim =苯并咪唑,dpdo = 4,4'-联吡啶-NN'-二氧化物,bpp = 1,3-bis (4-吡啶基)丙烷已制备,并通过元素分析,热重分析,红外光谱以及粉末和单晶X射线衍射进行了表征。化合物1显示了由3D Cu-ptz作为主体和Evans-Showell型聚氧阴离子[Co 2 Mo 10 H 4 O 38 ] 6-作为来宾组成的3D主体-来宾框架。化合物2由[Co 2 Mo 10 H 4 O38 ] 6 –聚氧阴离子和Cu-bim配位络合物形成2D共价层。化合物3还表现出基于通过Cu-dpdo配位基团连接的[Co 2 Mo 10 H 4 O 38 ] 6-聚氧阴离子的2D杂化网络。化合物4是一维双链结构,由[Co 2 Mo 10 H 4 O 38 ] 6–聚氧阴离子通过Na +和Cu 2+阳离子连接在一起。据我们所知,化合物1是第一个以Evans-Showell型多金属氧酸盐为客体的主客体化合物,化合物23是第一个由Evans-Showell型多金属氧酸盐构建的2D无机-有机杂化结构。化合物1 - 4是氧化还原催化剂,其非均相提示硫醚和醇的氧化以优异的效率。
更新日期:2017-09-18
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