Development of a rational synthetic pathways of porous materials by using polyoxometalates as building blocks

在我们的预研究中，[H_3V_<10>O_<28>]^&lt;3-&gt;形成了一个大的孢子，该孢子可以容纳水簇。在这个项目期间，我们成功地合成了可调有机小分子的多孔材料，其用途是[H_nV_<10>O_<28>]^&lt;（6-n）-&gt;阴离子和四烷基铵。对他们的晶体结构的分析揭示了对氢键的详细特征，其中表明了有机小分子进入这些离子晶体的多氧化物的吸收。对小聚氧化物酸盐的晶体结构分析， [V_4O_<12>]^&lt;4-&gt;，显示了它形成了一种能够适应水分子的晶体结构。四甲苯和水之间的氢结合被X射线差异实验清楚地观察到，展示了在四甲苯阴离子上支持的水分子可能是一个很好的分子模型，以支持金属氧化物的水分子。我们还研究了P之间的互动。 ... More 低氧化物和其低氧化状态中的过渡元素。We obtained crystals of Cu_3 V_<10>O_<28>·24 H_2 O and CuNa_4 V_<10>O_<28>·23 H_2 O。在这些系统中，我们在准备多孔材料方面并不成功，但我们发现，那些decavanadate的动画通过Cu^&lt;2+&gt;或Na^+方案连接在一起的一个维度链上。In the crystals of （CH_6N_3）_4Na_2H[PW_<11>O_<39>]·8H_2O， the [PW_<11>O_<39>]^&lt;7-&gt; anions were linked into one-dimensional chains through the Na^+ cations。这些例子展示了多氧化物复合材料的合理设计的可能性，这些材料将被展示出来的宏观物理化学性质。在这些研究中，我们介绍了SPring-8中的单晶体差测仪，并启用了高X射线吸收材料的精确结构分析。谢谢你的这一文书，对多氧化碳国家结构分析的精确度得到了显著的改进。This especially benefited the structure analysis of （CH_6N_3）_4Na_2H[PW_<11>O_<39>]·8H_2O， revealing the structural distortion of the [PW_<11>O_<39>]^&lt;7-&gt; anions due to the interaction with the Na^+ cations。Less（低）

In our preceding research, tetraphenylphosphonium salt of [H_3V_<10>O_<28>]^<3-> formed a large pore that accommodates a water cluster. During this project, we succeeded in synthesizing porous materials that can accommodate organic small molecules, by the use of [H_nV_<10>O_<28>]^<(6-n)-> anion and tetraalkylammonium cations. Analyses of their crystal structures revealed the detailed features of the hydrogen bonds which induces the incorporation of the organic small molecules into these ionic crystals of polyoxometalates. A crystal structure analysis of a smaller polyoxometalate, [V_4O_<12>]^<4->, showed that it forms a crystal with voids that can accommodate water molecules. The hydrogen bond between the tetravanadate and water was clearly observed by the X-ray diffraction experiment, which showed that the water molecules supported on the tetravanadate anion can be a good molecular model for the metal oxide supporting water molecules. We also investigated the interaction between the p … More olyoxometalates and the transition elements in their lower oxidation states. We obtained crystals of Cu_3V_<10>O_<28>・24H_2O and CuNa_4V_<10>O_<28>・23H_2O. In these systems, we were not successful in preparing porous materials, but we revealed that the decavanadate anions were linked into one-dimensional chains through the Cu^<2+> or Na^+ cations. In the crystals of (CH_6N_3)_4Na_2H[PW_<11>O_<39>]・8H_2O, the [PW_<11>O_<39>]^<7-> anions were linked into one-dimensional chains through the Na^+ cations. These exemplify the possibilities of the rational design of polyoxometalate composite material that would exhibit macroscopic physicochemical properties. In parallel with these studies, we introduced a single crystal diffractometer into SPring-8, which enabled the precise structure analyzes of highly x-ray absorbing materials. Thanks to this instrument, the precisions of the structure analyzes of polyoxotungstates were significantly improved. This especially benefited the structure analysis of (CH_6N_3)_4Na_2H[PW_<11>O_<39>]・8H_2O, revealing the structural distortion of the [PW_<11>O_<39>]^<7-> anions due to the interaction with the Na^+ cations. Less