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

以多金属氧酸盐为结构单元开发多孔材料的合理合成途径

• 批准号: 13640555
• 负责人: OZEKI Tomoji
• 金额: $ 2.24万
• 依托单位: Tokyo Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13640555/
• 关键词: polyoxometalates; crystal structure; porous material; x-ray diffraction; synchrotron radiation; incorporation of small molecules; ポリ酸; ポリバナジン酸; ポリタングステン酸; クリスタルデザイン; 結晶構造設計; 単結晶X線構造解析

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

在我们之前的研究中，[H_3V_<10>O_<28>]^<3->的四苯基磷盐形成了一个容纳水团簇的大孔隙。在本项目中，我们利用[H_nV_<10>O_<28>]^<(6-n)->阴离子和四烷基铵阳离子成功合成了可容纳有机小分子的多孔材料。对其晶体结构的分析揭示了氢键的详细特征，氢键诱导有机小分子结合到这些多金属氧酸盐离子晶体中。对一种较小的多金属氧酸盐[V_4O_<12>]^<4->的晶体结构分析表明，它形成了一种具有可容纳水分子的空隙的晶体。x射线衍射实验清楚地观察到四氰酸盐与水之间的氢键，表明四氰酸盐阴离子上负载的水分子可以作为金属氧化物负载水分子的良好分子模型。我们还研究了p…More多金属氧酸盐与低氧化态过渡元素之间的相互作用。我们得到Cu_3V_<10>O_<28>·24H_2O和CuNa_4V_<10>O_<28>·23H_2O的晶体。在这些体系中，我们没有成功地制备多孔材料，但我们发现十氰酸阴离子通过Cu^<2+>或Na^+阳离子连接成一维链。在（CH_6N_3）_4Na_2H[PW_<11>O_<39>]·8H_2O晶体中，[PW_<11>O_<39>]^<7->阴离子通过Na^+阳离子连接成一维链。这些例子说明了合理设计具有宏观物理化学性质的多金属酸氧酯复合材料的可能性。与这些研究同时，我们在SPring-8中引入了单晶衍射仪，使高x射线吸收材料的精确结构分析成为可能。该仪器的应用大大提高了多氧化钨酸盐结构分析的精度。这尤其有利于（CH_6N_3）_4Na_2H[PW_<11>O_<39>]·8H_2O的结构分析，揭示了[PW_<11>O_<39>]^<7->阴离子由于与Na^+阳离子的相互作用而产生的结构畸变。少

项目成果

Tomoji Ozeki, Katsuhiro Kusaka, Noritaka Honma, Yuji Nakamura, Setsuko Nakamura, Shunsuke Oike, Nobuhiro Yasuda, Hiroyuki Imura, Hidehiro Uekusa, Maiko Isshiki, Chuji Katayama, Yuji Ohashi: "Crystal Structure Analysis of a Hexatungstate by a High-Energy X

Tomoji Ozeki、Katsuhiro Kusaka、Noritaka Honma、Yuji Nakamura、Setsuko Nakamura、Shunsuke Oike、Nobuhiro Yasuda、Hiroyuki Imura、Hidehiro Uekusa、Maiko Isshiki、Chuji Katayama、Yuji Ohashi：“通过高能 X 射线对六钨酸盐进行晶体结构分析

Tomoji Ozeki, Noritaka Honma, Shunsuke Oike and Katsuhiro Kusaka , eds. by Toshihiro Yamase and Michael T. Pope: "Structure Determination of Polyoxotungstates Using High-Energy Synchrotron Radiation In "Polyoxometalate Chemistry for Nano-composite Design"

Tomoji Ozeki、Noritaka Honma、Shunsuke Oike 和 Katsuhiro Kusaka 编辑。

H.Nakano, T.Ozeki, A.Yagasaki: "Synthesis and Structural Characterization of a New Series of Vanadoselenites, [Se_xV_<4-x>O_<12-x>]^<(4-x)> (x=1,2)"Inorganic Chemistry. 40(8). 1816-1819 (2001)

H.Nakano、T.Ozeki、A.Yagasaki：“一系列新的钒硒酸盐的合成和结构表征，[Se_xV_<4-x>O_<12-x>]^<(4-x)> (x=1

Hiroyuki Nakano, Tomoji Ozeki, Atsushi Yagasaki: "Some Smaller Polyoxoanions. Their Synthesis and Characterization in Solution"Polyoxometalate chemistry for nano-composite design, T.Yamase and M.T.Pope, eds., Kluwer Academic/Plenum Publishers, New York, N

Hiroyuki Nakano、Tomoji Ozeki、Atsushi Yagasaki：“一些较小的多氧阴离子。它们在溶液中的合成和表征”用于纳米复合材料设计的多金属氧酸盐化学，T.Yamase 和 M.T.Pope，编辑，Kluwer 学术/Plenum 出版社，纽约，N

Hiroyuki Nakano, Tomoji Ozeki, Atsushi Yagasaki: "Some Smaller Polyoxoanions. Their Synthesis and Characterization in Solution""Polyoxometalate Chemistry for Nano-composite Design" Toshihiro Yamase and Michael T.Pope, Eds., Kluwer Academic/Plenum Publishe

Hiroyuki Nakano、Tomoji Ozeki、Atsushi Yagasaki：“一些较小的多氧阴离子。它们在溶液中的合成和表征”“纳米复合材料设计中的多金属氧酸盐化学” Toshihiro Yamase 和 Michael T.Pope，编辑，Kluwer 学术/Plenum Publishe