From 0D dimer to 2D network-supramolecular assembly of organic derivatized polyoxometalates with remote hydroxyl via hydrogen bonding.
From 0D dimer to 2D network-supramolecular assembly of organic derivatized polyoxometalates with remote hydroxyl via hydrogen bonding.
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DOI：
10.1021/ic900985w
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发表时间：
2009-08
影响因子：
4.6
通讯作者：
Longsheng Wang;Li Zhu;Panchao Yin;W. Fu;Jiake Chen;J. Hao;Fengping Xiao;Chunlin Lv;Jin Zhang;Lu Shi;Qiang Li;Yongge Wei
中科院分区：
文献类型：
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作者：
Longsheng Wang;Li Zhu;Panchao Yin;W. Fu;Jiake Chen;J. Hao;Fengping Xiao;Chunlin Lv;Jin Zhang;Lu Shi;Qiang Li;Yongge Wei
六钼酸盐的一系列远程羟基官能化的有机酰亚胺衍生物（Bu（4）N）（2）[Mo（6）O（18）（克雷斯）]（1）（克雷斯= 4-氨基间甲酚），（Bu（4）N）（2）[Mo（6）O（17）（克雷斯）（2）] x H（2）O（2），（Bu（4）N）（2）[Mo（6）O（18）（Phen）] x i-PrOH（Phen =对氨基苯酚）（3）、（Bu（4）N）（2）[Mo（6）O（18）（Phen）] x EtOH（4）、（Bu（4）N）（2）[Mo（6）O（17）（Phen）（2）]（5）、（Bu（4）N）（2）[Mo（6）O（18）（Naph）]合成了（Naph = 5-氨基-1-萘炔基）（6）和（Bu（4）N）（2）[Mo（6）O（18）（Chex）] x1.5H（2）O（Chex = trans-4-aminocyclohexanol）（7），并通过单晶X射线衍射、红外光谱、紫外可见光谱、元素分析、核磁共振氢谱和循环伏安法进行了表征。X射线结构研究表明，分子间和分子内氢键在其超分子组装过程中起着重要作用，发现（i）六钼酸根簇的桥联配体比末端配体更倾向于形成氢键作为受体;（ii）具有氢键供体和受体的小溶剂分子，例如水、i-PrOH和EtOH，通常在它们的超分子组装体中充当氢键桥;（3）氢键作用对阴离子构象的影响除细胞堆积外，还有重要作用;（iv）化合物1-7的氢键超分子组装表现出有趣的变化，从二聚体（3）到一维无限单链（4），到一维无限双链（2），再到二维网络（1、5、6和7），这是由于接枝有机配体、取代数和结晶溶剂分子的改变。为了探索它们在导电性方面的潜在应用，化合物1-7的光学带隙根据它们的固态反射光谱来确定。本研究不仅系统地研究了羟基官能化的六钼酸酯的氢键相互作用和超分子组装，而且为进一步的修饰（包括酯化）提供了一些可用的前体。
A series of remote hydroxyl functionalized organoimido derivatives of hexamolybdate, (Bu(4)N)(2)[Mo(6)O(18)(Cres)] (1) (Cres = 4-amino-m-cresol), (Bu(4)N)(2)[Mo(6)O(17)(Cres)(2)] x H(2)O (2), (Bu(4)N)(2)[Mo(6)O(18)(Phen)] x i-PrOH (Phen = p-aminophenol)(3), (Bu(4)N)(2)[Mo(6)O(18)(Phen)] x EtOH (4), (Bu(4)N)(2)[Mo(6)O(17)(Phen)(2)] (5), (Bu(4)N)(2)[Mo(6)O(18)(Naph)] (Naph = 5-amino-1-napheynyl) (6), and (Bu(4)N)(2)[Mo(6)O(18)(Chex)] x 1.5 H(2)O (Chex = trans-4-aminocyclohexanol) (7) were synthesized and characterized by single crystal X-ray diffraction, FT-IR spectra, UV-vis spectra, elemental analysis, (1)H NMR, and cyclic voltammetry. X-ray structural study reveals that intermolecular and intramolecular hydrogen bonding plays an important role in their supramolecular assembly; it is found that (i) bridged oxo ligands of hexamolybdate cluster are more inclined to form hydrogen bonds as acceptors than terminal oxo ligands in this system; (ii) small solvent molecules with hydrogen bonding donor and acceptor, such as water, i-PrOH, and EtOH, usually act as hydrogen bonding bridge in their supramolecular assembly; (iii) hydrogen bonding has an important influence on their anion conformation besides cell packing; (iv) the hydrogen bonding supramolecular assembly of compounds 1-7 demonstrate an interesting change from dimer (3), to 1D infinite single chain (4), to 1D infinite double chain (2), and to 2D network (1, 5, 6, and 7) owing to the alteration of the grafting organic ligand, the substituted number, and the crystallized solvent molecule. To explore their potential application in conductivity, the optical band gap of compounds 1-7 were determined upon their solid state reflectance spectra. Our current study not only surveys systematically hydrogen bonding interaction and supramolecular assembly of remote hydroxyl functionalized organoimido-derivatized hexamolybdates but also provides some available precursors for further modification including esterification.