A new sandwiched polyoxometalate [HK11Cd4Cl2（PW9034）2]·18H2O （1）, incor- porating a unique hybrid tetranuclear cadmium cluster （abbreviated to {Cd4}） with two trivacant polyanions [B-α-PW9O34]9-, has been ...A new sandwiched polyoxometalate [HK11Cd4Cl2（PW9034）2]·18H2O （1）, incor- porating a unique hybrid tetranuclear cadmium cluster （abbreviated to {Cd4}） with two trivacant polyanions [B-α-PW9O34]9-, has been hydrothermally synthesized and structurally characterized by elemental analyses, IR spectroscopy, UV-vis, and single-crystal X-ray diffraction analysis. Crystal data for 1： monoclinic, space group C2/c, a = 19.2997（4）, b = 13.8014（3）, c = 31.9819（8） A, β = 102.764（2）°, V= 8308.3（3） A3, Z = 4, P2O86Cl2K11Cd4W18H37, Mr = 5735.13, Dc = 4.584 mg-mm-3, F（000） = 10084, μ = 26.579 mm-1, the final R = 0.0378 and wR = 0.0989 for 6558 observed reflections （I〉 2σ（I））. X-ray crystallographic study shows that the molecular structure of 1 contains four cadmium atoms. Two CdO6 distorted octahedra and two CdOsC1 distorted octahedra combine with each other in turn via edge-sharing, resulting in a regular rhomb-like cluster sandwiched between two {B-a-PW9034} units. Further, the sandwich-type polyoxoanions were connected by K＋ ions to form a complicated 3-D open-framework through connecting with each terminal O atom of the [Cd4C12（PW9O34）2]12- polyoxoanions. In addition, compound 1 exhibits photoluminescence property at room temperature and the band gap can be assessed at 3.25 eV.展开更多
Cluster-assembled materials(CAMs)present delicate structures and tailored properties,which have gained extensive interest in recent years.Due to the noncovalent linkage and size of sub-1 nm,clusters present polymer-li...Cluster-assembled materials(CAMs)present delicate structures and tailored properties,which have gained extensive interest in recent years.Due to the noncovalent linkage and size of sub-1 nm,clusters present polymer-like solution behaviors distinct from conventional nanocrystals,whereby a variety of CAMs with different constructions have been fabricated.To our knowledge,the morphologies and properties of CAMs are closely connected,which are strongly dependent on the structure and coordination state of cluster building blocks.For the CAMs with superior performances,the specific arrangement and surroundings of clusters at subnanometer scale usually result in wellorganized structures.In this review,we will summarize the recent progress of CAMs with highly ordered structures and advanced properties,where polyoxometalate cluster assemblies as well as cluster-nuclei co-assemblies are involved.The application potentials of CAMs are then discussed,especially on the cluster arrangements and interactions at subnanometer scale.However,current researches are far from reaching the point,and future efforts are needed before the nature of cluster-based nanostructures can be sufficiently revealed.We hope this article can offer unique insights and instructive understanding to the CAMs.展开更多
基金Supported by theNNSFC(No.51108122)Open Project of State Key Laboratory of Urban Water Resource and Environment,Harbin Institute of Technology(No.QA201025)+1 种基金Fundamental Research Funds for the Central Universities(No.HIT.NSRIF.2010053)Science and Technology Innovation Talents Special Foundation of Harbin(2010RFQXG035 and 2007RFXXG018)
文摘A new sandwiched polyoxometalate [HK11Cd4Cl2（PW9034）2]·18H2O （1）, incor- porating a unique hybrid tetranuclear cadmium cluster （abbreviated to {Cd4}） with two trivacant polyanions [B-α-PW9O34]9-, has been hydrothermally synthesized and structurally characterized by elemental analyses, IR spectroscopy, UV-vis, and single-crystal X-ray diffraction analysis. Crystal data for 1： monoclinic, space group C2/c, a = 19.2997（4）, b = 13.8014（3）, c = 31.9819（8） A, β = 102.764（2）°, V= 8308.3（3） A3, Z = 4, P2O86Cl2K11Cd4W18H37, Mr = 5735.13, Dc = 4.584 mg-mm-3, F（000） = 10084, μ = 26.579 mm-1, the final R = 0.0378 and wR = 0.0989 for 6558 observed reflections （I〉 2σ（I））. X-ray crystallographic study shows that the molecular structure of 1 contains four cadmium atoms. Two CdO6 distorted octahedra and two CdOsC1 distorted octahedra combine with each other in turn via edge-sharing, resulting in a regular rhomb-like cluster sandwiched between two {B-a-PW9034} units. Further, the sandwich-type polyoxoanions were connected by K＋ ions to form a complicated 3-D open-framework through connecting with each terminal O atom of the [Cd4C12（PW9O34）2]12- polyoxoanions. In addition, compound 1 exhibits photoluminescence property at room temperature and the band gap can be assessed at 3.25 eV.
基金National Natural Science Foundation of China,Grant/Award Number:22035004National Key R&D Program of China,Grant/Award Numbers:2016YFA0202801,2017YFA0700101。
文摘Cluster-assembled materials(CAMs)present delicate structures and tailored properties,which have gained extensive interest in recent years.Due to the noncovalent linkage and size of sub-1 nm,clusters present polymer-like solution behaviors distinct from conventional nanocrystals,whereby a variety of CAMs with different constructions have been fabricated.To our knowledge,the morphologies and properties of CAMs are closely connected,which are strongly dependent on the structure and coordination state of cluster building blocks.For the CAMs with superior performances,the specific arrangement and surroundings of clusters at subnanometer scale usually result in wellorganized structures.In this review,we will summarize the recent progress of CAMs with highly ordered structures and advanced properties,where polyoxometalate cluster assemblies as well as cluster-nuclei co-assemblies are involved.The application potentials of CAMs are then discussed,especially on the cluster arrangements and interactions at subnanometer scale.However,current researches are far from reaching the point,and future efforts are needed before the nature of cluster-based nanostructures can be sufficiently revealed.We hope this article can offer unique insights and instructive understanding to the CAMs.
