Assembly of [(eta5-C5Me5)MoS3Cu3]-supported one-dimensional chains with single, double, triple, and quadruple strands.
Assembly of [(eta5-C5Me5)MoS3Cu3]-supported one-dimensional chains with single, double, triple, and quadruple strands.
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DOI：
10.1021/ic8003454
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发表时间：
2008-05
影响因子：
4.6
通讯作者：
Wenhao Zhang;Ying-Lin Song;Zhen-hong Wei;Ling-Ling Li-Ling;Yu-Jian Huang;Yong Zhang;J. Lang
中科院分区：
文献类型：
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作者：
Wenhao Zhang;Ying-Lin Song;Zhen-hong Wei;Ling-Ling Li-Ling;Yu-Jian Huang;Yong Zhang;J. Lang
本文报道了一组新的[（eta_5-C_5Me_5）MoS_3Cu_3]基超分子化合物的结构，这些化合物是由两个预形成的簇[PPh_4][（eta_5-C_5Me_5）MoS_3（CuX）_3]（X = Br（1a），NCS（1b））与1，2-双（4-吡啶基）乙烷（bpe）和1，3-双（4-吡啶基）丙烷（bpp）的一维（1D）排列组成的. 1a与bpe在不同摩尔比下反应，（[（（η 5-C5Me5）MoS3Cu3）2（μ-bpe）3.5Br4]·MeCN）n（2），（[（（η 5-C5Me5）MoS3Cu3）2（μ-bpe）3Br4].Sol）n（3a：溶胶= DMSO. 3 MeCN; 3b：溶胶= 2苯胺.3MeCN），（[（（η 5-C5Me5）MoS3Cu3）2（mu-bpe）3（bpe）Br4].0.35DMF）n（4）和（[（（η 5-C5Me5）MoS3Cu3）2（mu-bpe）2（mu-Br）（mu3-Br）Br2].DMF.MeCN）n（5）。另一方面，用bpp处理1a或1b产生[（eta 5-C5 Me 5）MoS 3Cu 3（mu-bpp）（mu-Br）Br]n（6）和（[（（eta 5-C5 Me 5）MoS 3Cu 3）2（mu-bpp）3（mu-NCS）2（NCS）]（NCS））n（7）。化合物2-7通过元素分析、紫外-可见光谱、红外光谱、核磁共振氢谱和X射线衍射进行了表征。在2中，每个[（eta 5-C5 Me 5）MoS 3Cu 3]芯作为一个角形的两连接节点，通过单、双bpe桥连接其他等效芯，形成一维“长城”状链。在3a和3b中，[（η 5-C5 Me 5）MoS 3Cu 3]核通过单bpe桥和双bpe桥交替连接，得到一维锯齿形链。在4中，六个簇核（两个作为两连接节点，四个作为三连接节点）通过四个单bpe和两个双bpe桥连接，形成环己烷形重复单元，该单元进一步与其他单元融合，生成一维双链。化合物5具有简单的一维锯齿形链，由单个bpe桥连接的簇核组成。在6中，团簇核心通过单bpp桥连接，得到一维螺旋链，该螺旋链进一步通过C-H连接两个螺旋相关链。Br氢键相互作用，从而形成一维氢键三链。化合物7具有罕见的一维四重链，其中[（eta 5-C5 Me 5）MoS 3Cu 3]核作为平面四和五连接节点，通过单bpp桥和单和双硫氰酸盐桥将其他等效核连接起来。此外，还利用Z扫描技术，在波长为532 nm，脉冲宽度为4.5 ns的激光作用下，研究了1a，2，3a和4-7在苯胺溶液中的三阶非线性光学性质。
The construction of a new set of [(eta5-C5Me5)MoS3Cu3]-based supramolecular compounds with different one-dimensional (1D) arrays from two preformed clusters [PPh4][(eta5-C5Me5)MoS3(CuX)3] (X = Br (1a), NCS (1b)) with 1,2-bis(4-pyridyl)ethane (bpe) and 1,3-bis(4-pyridyl)propane (bpp) is presented. Reactions of 1a with bpe in different molar ratios afforded ([((eta5-C5Me5)MoS3Cu3) 2(mu-bpe)3.5Br4].MeCN) n (2), ([((eta5-C5Me5)MoS3Cu3)2(mu-bpe)3Br4].Sol)n (3a: Sol = DMSO.3MeCN; 3b: Sol = 2aniline.3MeCN), ([((eta5-C 5Me5)MoS3Cu3)2(mu-bpe)3(bpe)Br4].0.35DMF)n (4), and ([((eta5-C5Me5)MoS3Cu3)2(mu-bpe)2(mu-Br)(mu3-Br)Br2].DMF.MeCN)n (5). On the other hand, treatment of 1a or 1b with bpp produced [(eta5-C5Me5)MoS3Cu3(mu-bpp)(mu-Br)Br]n (6) and ([((eta5-C5Me5)MoS3Cu3)2(mu-bpp)3(mu-NCS)2(NCS)](NCS))n (7). Compounds 2-7 have been characterized by elemental analysis, UV-vis spectroscopy, IR spectroscopy, 1H NMR, and X-ray analysis. In 2, each [(eta5-C5Me5)MoS3Cu3] core serves as an angular two-connecting node to link other equivalent cores by single and double bpe bridges to form a 1D "Great Wall"-like chain. In 3a and 3b, the [(eta5-C5Me5)MoS3Cu3] cores are linked alternatively by single and double bpe bridges to give a 1D zigzag chain. In 4, six cluster cores (two as a two-connecting node and four as a three-connecting node) are connected by four single bpe and two double bpe bridges to form a cyclohexane-shaped repeating unit, which is further fused with other units to generate a 1D double-stranded chain. Compound 5 has a simple 1D zigzag chain consisting of the cluster cores linked by single bpe bridges. In 6, the cluster cores are linked by single bpp bridges to give a 1D helical chain, which further holds two symmetry-related chains through C-H...Br hydrogen-bonding interactions, thereby forming a 1D H-bonded triple-stranded chain. Compound 7 has a rare 1D quadruple chain, in which the [(eta5-C5Me5)MoS3Cu3] cores work as planar four- and five-connecting nodes to interconnect other equivalent cores through single bpp bridges and single and double thiocyanate bridges. In addition, the third-order nonlinear optical properties of 1a, 2, 3a, and 4-7 in aniline were also investigated by using the Z-scan technique with a 4.5 ns pulse laser at 532 nm.