由铜（II）多面体畸变驱动的六铜取代多金属氧酸盐的组合化学：从四聚体、一维链到三维框架。

Combination chemistry of hexa-copper-substituted polyoxometalates driven by the Cu(II)-polyhedra distortion: from tetramer, 1D chain to 3D framework.

作者信息

Li Bing, Zhao Jun-Wei, Zheng Shou-Tian, Yang Guo-Yu

机构信息

State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, China.

出版信息

Inorg Chem. 2009 Sep 7;48(17):8294-303. doi: 10.1021/ic900931r.

DOI:10.1021/ic900931r

PMID:19634865

Abstract

Reaction of CuCl(2) x 2 H(2)O and trivacant Keggin polyoxoanion Na(9)[A-alpha-PW(9)O(34)] x 7 H(2)O in the presence of ethylene-diamine/1,2-diaminopropane (en/enMe) under hydrothermal conditions led to five novel inorganic-organic hybrid polyoxotungstates (POTs):Cu(en)(2)Cu(en)(2)(H(2)O)[Cu(H(2)O)(2)][Cu(4)(H(2)O)(2)(B-alpha-PW(9)O(34))(2)] x 2 H(2)O(1), [Cu(6)(mu(3)-OH)(3)(en)(3)(H(2)O)(5)(B-alpha-PW(9)O(34))] x 6 H(2)O (2), Na(6){Cu(6)(mu(3)-OH)(3)(en)(3)(H(2)O)(2)(B-alpha-PW(9)O(34))[Cu(4)(H(2)O)(2)(B-alpha-PW(9)O(34))(2)]} x 2 H(2)en x 8 H(2)O (3), [Cu(6)(mu(3)-OH)(3)(en)(3)(H(2)O)(3)(B-alpha-PW(9)O(34))] x 4 H(2)O (4), [Cu(II)(6)Cu(I)(4)(mu(6)-O)(OH)(18)]Cu(6)(mu(3)-OH)(3)(enMe)(3)(H(2)O)(3)(B-alpha-PW(9)O(34)) x 4 H(3)O x 2 H(2)O (5). 1 is a new 1D chain constructed from alternate tetra-Cu(II) sandwiched units Cu(II)(4)(H(2)O)(2)(B-alpha-PW(9)O(34))(2) and dinuclear Cu(II)(2)(H(2)O)(6) units. 2-5 are a series of novel transition-metal substituted polyoxometalates (TMSPs) comprising hexa-Cu(II) substituted {Cu(6)PW(9)} units (Cu(6) = Cu(6)(mu(3)-OH)(3), PW(9) = B-alpha-PW(9)O(34), Scheme 1). 2 is an unusual monomer. 3 is an unprecedented tetramer built by two types of TMSP units, [Cu(6)PW(9)(en)(3)(H(2)O)(2)] and Cu(II)(4)(H(2)O)(2)(PW(9))(2). 4 is a novel chain assembled from [Cu(6)PW(9)(en)(3)(H(2)O)(3)] units by double-bridging mode. Most interestingly, 5 is a open framework made by [Cu(6)PW(9)(enMe)(3)(H(2)O)(3)] units, in which the novel decacopper oxygen clusters, Cu(I)(4)Cu(II)(6)(mu(6)-O)(OH)(18) formed in situ, are encapsulated into the channels, and 5 represents the first decametallic-cluster-containing open framework built by TMSP units. 2-5 all contain the hexa-Cu(II) substituted POT unit {Cu(6)PW(9)L(3)(H(2)O)(n)} (L = en/enMe, n < 6) made by {Cu(6)L(3)(H(2)O)(n)} core and trivacant Keggin PW(9) fragments. Moreover, 3-5 can be viewed as combining derivatives of 2 through substituting water ligands on hexa-Cu(II) {Cu(6)L(3)(H(2)O)(n)} units by terminal oxygen atoms of PW(9) units. Importantly, the Cu(II)-polyhedra Jahn-Tell/pseudo-Jahn-Teller distortion plays a crucial role in the formation of 1-5. The magnetic behaviors of 2-5 show antiferromagnetic interactions between the Cu(II) ions in the hexa-Cu(II) cluster.

摘要

在水热条件下，氯化铜二水合物（CuCl₂·2H₂O）与三缺位Keggin型多金属氧酸盐Na₉[A-α-PW₉O₃₄]·7H₂O在乙二胺/1,2-二氨基丙烷（en/enMe）存在下反应，得到了五种新型无机-有机杂化多金属钨酸盐（POTs）：[Cu(en)₂]₂[Cu(en)₂(H₂O)]₂[Cu(H₂O)₂][Cu₄(H₂O)₂(B-α-PW₉O₃₄)₂]·2H₂O（1）、[Cu₆(μ₃-OH)₃(en)₃(H₂O)₅(B-α-PW₉O₃₄)]·6H₂O（2）、Na₆{[Cu₆(μ₃-OH)₃(en)₃(H₂O)₂(B-α-PW₉O₃₄)]₂[Cu₄(H₂O)₂(B-α-PW₉O₃₄)₂]}·2H₂en·8H₂O（3）、[Cu₆(μ₃-OH)₃(en)₃(H₂O)₃(B-α-PW₉O₃₄)]·4H₂O（4）、[Cu(II)₆Cu(I)₄(μ₆-O)(OH)₁₈][Cu₆(μ₃-OH)₃(enMe)₃(H₂O)₃(B-α-PW₉O₃₄)]₄·4H₃O·2H₂O（5）。1是由交替的四核Cu(II)夹心单元[Cu(II)₄(H₂O)₂(B-α-PW₉O₃₄)₂]¹⁰⁻和双核[Cu(II)₂(H₂O)₆]⁴⁺单元构建的新型一维链。2 - 5是一系列新型过渡金属取代多金属氧酸盐（TMSPs），包含六核Cu(II)取代的{Cu₆PW₉}单元（Cu₆ = Cu₆(μ₃-OH)₃，PW₉ = B-α-PW₉O₃₄，方案1）。2是一种不寻常的单体。3是由两种类型的TMSP单元[Cu₆PW₉(en)₃(H₂O)₂]和[Cu(II)₄(H₂O)₂(PW₉)₂]¹⁰⁻构建的前所未有的四聚体。4是由[Cu₆PW₉(en)₃(H₂O)₃]单元通过双桥连模式组装而成的新型链。最有趣的是,5是由[Cu₆PW₉(enMe)₃(H₂O)₃]单元构成的开放框架，其中原位形成的新型十核铜氧簇[Cu(I)₄Cu(II)₆(μ₆-O)(OH)₁₈]⁴⁻被封装在通道中，5代表了第一个由TMSP单元构建的含十金属簇的开放框架。2 - 5都包含由{Cu₆L₃(H₂O)ₙ}核和三缺位Keggin PW₉片段构成的六核Cu(II)取代的POT单元{Cu₆PW₉L₃(H₂O)ₙ}（L = en/enMe，n < 6）。此外，3 - 5可以看作是通过用PW₉单元的端基氧原子取代六核Cu(II) {Cu₆L₃(H₂O)ₙ}单元上的水配体而从2衍生而来的组合衍生物。重要的是，Cu(II) - 多面体的Jahn - Tell/假Jahn - Teller畸变在1 - 5的形成中起关键作用。2 - 5的磁行为表明六核Cu(II)簇中的Cu(II)离子之间存在反铁磁相互作用。