A multifunctional metal-organic open framework with a bcu topology constructed from undecanuclear clusters.
A multifunctional metal-organic open framework with a bcu topology constructed from undecanuclear clusters.
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DOI：
10.1002/anie.200601668
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发表时间：
2006-09
影响因子：
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通讯作者：
Q. Fang;G. Zhu;Zhao Jin;Ming Xue;Xiao Wei;Dejun Wang;S. Qiu
中科院分区：
文献类型：
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作者：
Q. Fang;G. Zhu;Zhao Jin;Ming Xue;Xiao Wei;Dejun Wang;S. Qiu
6126 2006 Wiley-VCH Verlag GmbH & Co. KGaA，魏因海姆Angew. Chem.Int.Ed.2006，45，6126-6130电子效应已经成为追求多功能材料的主要挑战之一。[2-4]例如，Yaghi及其同事报道了在三乙胺存在下由硝酸铽和1，4-苯二甲酸（H2 bdc）合成[Tb 2-（bdc）3]· 4 H2O，其具有扩展结构（孔体积：0.099 cm 3 gcm-1），并研究了其发光寿命。[2a]关于多孔和磁性的多功能材料的研究，Riou，Fredrey及其同事合成了杂化有机-无机固体[V（OH）（bdc）]·xH 2bdc（x% 0.75），其具有非常大的孔隙（BET表面积：930（30）m2 gt 1）和良好的磁特性（反铁磁性低于95 K），通过使用含有离域π电子的刚性有机链接器连接链的角共享钒为中心的八面体。[3a]本课题组成功地制备了一种新型的三维非互穿多功能有机玻璃[Zn 7 O2（bda）5（H2O）2]·5DMF· 4 EtOH· 6 H2O（H2 bda = 1，4-苯二丙烯酸; DMF=二甲基甲酰胺），它由七核羧酸锌二级结构单元（SBU）构成，包含一个间距约为17.3的交叉孔道系统。该化合物表现出优异的吸附、H2储存和光电性能。[4]我们制备新型多功能结构的策略是构建金属羧酸盐SBU。金属羧酸盐簇SBU的构建已被证明是制备新一代高度多孔MOFs的有效和强大的合成方法。[5，6]有趣的是，Powell及其同事率先研究了含有柔性配体hpdta（H5 hpdta = HOCH 2 [CH 2N-（CH 2COOH）2] 2）的Al 15簇聚集体的铝配体单元，如[Al 15（μ3-O）4（μ3-OH）6（μ-OH）14-（hpdta）4] 3 H。[7]然而，尽管已经合成了许多由不同的过渡金属羧酸盐簇SBU构建的MOF，但它们通常由双核、三核或四核金属羧酸盐簇组成，其中水分子作为桥接配体发挥重要作用。[8]由桥接水分子结合在一起的金属中心的数量受到其弱配位能力的限制。为了克服这一困难，我们的策略是用具有强配位能力的甲酸（HCOOH）取代桥接水分子，构建稳定的金属羧酸盐簇SBU。作为我们设计原理的一个例子，本文描述了由十一核簇合物[Cd 11（μ4-HCOO-4）6（bpdc）9]·9DMF· 6 H2O（1; H2 bpdc = 4，4 '-biphenyldicarboxylic acid）构建的大孔开放骨架配合物的合成、结构、吸附和光电性质。据我们所知，该MOF具有迄今为止报道的最大的过渡金属羧酸盐簇SBU。聚合物1在温和条件下通过仔细调节刚性（bpdc）和柔性（HCOOH）配体的相对量来合成。X射线晶体学显示，1在三方晶系中结晶（空间群R3 c（编号161））。[9]1结构中的所有镉原子都具有八面体配位环境。如图1a所示，CdII中心八面体通过来自bpdc阴离子的18个羧酸根基团连接在一起，其以二齿或螯合/桥接二齿方式结合，和六个μ4-HCOOH 4基团构建纳米十一核{Cd 11（μ4-HCOOH 4）6（CO2）18}团簇，具有C3对称性，尺寸约为10.5 11.5 12.8 3（在...
6126 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Angew. Chem. Int. Ed. 2006, 45, 6126–6130 electronic effects has become one of the major challenges in the pursuit of multifunctional materials.[2–4] Yaghi and coworkers, for example, have reported the synthesis of [Tb2-(bdc) 3]· 4 H2O, which has an extended structure (pore volume: 0.099 cm3 gÀ1), from terbium nitrate and 1, 4-benzenedicarboxylic acid (H2bdc) in the presence of triethylamine, and have investigated its luminescence lifetime.[2a] As for the study of multifunctional materials that are both porous and magnetic, Riou, FØrey, and co-workers have synthesized the hybrid organic–inorganic solid [V (OH)(bdc)]· xH2bdc (x% 0.75), which has very large pores (BET surface area: 930 (30) m2 gÀ1) and good magnetic characteristics (antiferromagnetic below 95 K), by using rigid organic linkers containing delocalized π electrons to connect chains of cornersharing vanadium-centered octahedra.[3a] Our group has successfully prepared the novel 3D noninterpenetrating MOF [Zn7O2 (bda) 5 (H2O) 2]· 5 DMF· 4 EtOH· 6 H2O (H2bda= 1, 4-benzenediacrylic acid; DMF= dimethylformamide), which is constructed from heptanuclear zinc carboxylate secondary building units (SBUs) and contains an intersecting channel system with a spacing of approximately 17.3. This compound exhibits excellent adsorption, H2 storage, and photoelectronic properties.[4] Our strategy for preparing novel multifunctional structures is to construct metal carboxylate SBUs. The construction of metal carboxylate cluster SBUs has been demonstrated to be an effective and powerful synthetic method to produce a new generation of highly porous MOFs.[5, 6] Interestingly, Powell and co-workers have pioneered studies on aluminum–ligand units with Al15 cluster aggregates containing the flexible ligand hpdta (H5hpdta= HOCH2 [CH2N-(CH2COOH) 2] 2), such as [Al15 (μ3-O) 4 (μ3-OH) 6 (μ-OH) 14-(hpdta) 4] 3À.[7] However, although many MOFs built from different transition-metal carboxylate cluster SBUs have been synthesized, they usually consist of di-, tri-, or tetranuclear metal carboxylate clusters, in which a water molecule plays an important role as a bridging ligand.[8] The number of metal centers held together by the bridging water molecule is limited by its weak coordination ability. To overcome this difficulty, our strategy is to substitute the bridging water molecule with formic acid (HCOOH), which has a strong coordination ability, to construct stable metal carboxylate cluster SBUs. As an example of our design principle, we describe herein the synthesis and structure, as well as the sorption and optoelectronic properties of the large-pore open-framework complex[Cd11 (μ4-HCOOÀ) 6 (bpdc) 9]· 9 DMF· 6 H2O (1; H2bpdc= 4, 4’-biphenyldicarboxylic acid), which is constructed from undecanuclear clusters. To our knowledge, this MOF has the largest transition-metal carboxylate cluster SBUs reported to date. Polymer 1 was synthesized under mild conditions by carefully adjusting the relative quantities of the rigid (bpdc) and flexible (HCOOH) ligands. X-ray crystallography revealed that 1 crystallizes in the trigonal system (space group R3c (no. 161)).[9] All of the cadmium atoms in the structure of 1 have octahedral coordination environments. As shown in Figure 1a, the CdII-centered octahedra are linked together by 18 carboxylate groups from bpdc anions, which bind in a didentate or a chelating/bridging didentate fashion, and six μ4-HCOOÀ moieties to build up a nanosized undecanuclear {Cd11 (μ4-HCOOÀ) 6 (CO2) 18} cluster with C3 symmetry and dimensions of approximately 10.5 11.5 12.8 3 (measured between …