Structures and properties of weakly associated polyoxometalate-transition metal complexes

弱缔合多金属氧酸盐-过渡金属配合物的结构和性能

• 批准号: 15550047
• 负责人: OZEKI Tomoji
• 金额: $ 2.37万
• 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: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15550047/
• 关键词: polyoxometalates; transition metal ions; x-ray diffraction; crystal structure; synchrotron radiation; non-linear optical properties; protonation; イオン結晶; 結晶工学; ナノ材料; 分子性固体; 分子認識; 単結晶X線構造解析; ポリカチオン; ポリタングステン酸; ポリバナジン酸; 巨大球状分子; ポリモリブデン酸

This research project aims at synthesizing complexes of polyoxometalates with transition metal ions, analyzing their crystal structures, and then examining the physicochemical properties that are specific to their structures. First, the magnetic properties of [Cu_2(OH)_2(OH_2)_6][Cu_2(OH_2)_8][V_<10>O_<28>]-4(CH_3)_2CO, which was first synthesized and characterized by the investigator, were investigated. The compound has two pairs of Cu^<2+> cations on the two sides of the [V_<10>O_<28>]^<6-> core, which are separated by 2.89 Å and 3.37 Å, respectively. The unpaired electrons of these pairs were not coupled and each Cu^<2+> atom works as an independent spin center. Second, double salts of [V_<10>O_<28>]^<6-> with Cu^<2+> and NH_4^+, K^+ or Rb^+ were synthesized and their crystal structures were determined. In these crystals, a water molecule coordinating to the cation supports a hydrogen atom on the [V_<10>O_<28>]^<6-> core via hydrogen bond and stabilizes a monoprotonated species, [HV … More _<10>_O<28>]^<5->. In these crystals, the precise location of the protons on the monoprotonated decavanadate anion was first determined unambiguously. Also, the structure determination of [SiW_<11>O_<39>]^<8-> crystallized with Na^+ and guanidinium cations revealed that the compound exhibits a novel screw structure of [SiW_<11>O_<39>]^<8-> linked by Na^+ cation, although transition metals were not incorporated into the compound. Its structure indicated a possibility that it would show non-linear optical properties and thus pulsed laser light with the wavelength of 800 nm was irradiated, resulting in the observation of second harmonic generation. In parallel with these studies, the investigator has installed and upgraded diffractometers at two synchrotron facilities : SPring-8 and Photon Factory of High Energy Accelerator Research Organization. These efforts have profited the precise structure analyses of abovementioned NLO active silicotungstate crystals as well as the structural elucidation of the molecular growth and intermolecular condensation of mixed valence molybdenum giant clusters with nanometer sized ring shape. Less

本课题旨在合成具有过渡金属离子的多金属氧酸盐配合物，分析其晶体结构，并研究其结构特有的物理化学性质。首先，对研究者首次合成并表征的[Cu_2(OH)_2(OH_2)_6][Cu_2(OH_2)_8][V_<10>O_<28>]-4(CH_3)_2CO的磁性能进行了研究。该化合物在[V_<10>O_<28>]^<6->核两侧有两对Cu^<2+>阳离子，它们的间距分别为2.89 Å和3.37 Å。这些电子对中的未配对电子没有耦合，每个Cu^<2+>原子作为一个独立的自旋中心工作。其次，合成了Cu^<2+>和NH_4^+、K^+或Rb^+的[V_<10>O_<28>]^<6->双盐，并测定了它们的晶体结构。在这些晶体中，与阳离子配位的水分子通过氢键将氢原子支撑在[V_<10>O_<28>]^<6->核上，并稳定了单质子化物质[HV…More _<10>_O<28>]^<5->。在这些晶体中，质子在单质子化的十氰酸阴离子上的精确位置首次被明确地确定。同时，对[SiW_<11>O_<39>]^<8->与Na^+和胍离子结晶的结构测定表明，该化合物具有Na^+阳离子连接的[SiW_<11>O_<39>]^<8->的新型螺旋结构，但未掺入过渡金属。它的结构表明它有可能呈现非线性光学性质，因此照射波长为800 nm的脉冲激光，观察到二次谐波的产生。在进行这些研究的同时，研究者还在两个同步加速器设施：spring8和高能加速器研究组织的光子工厂安装和升级了衍射仪。这些工作有助于对上述NLO活性硅钨酸盐晶体进行精确的结构分析，以及对具有纳米尺寸环状的混合价钼巨团簇的分子生长和分子间缩聚的结构阐明。少

项目成果

The Fifth Series of Experimental Chemistry, Vol.11

实验化学第五辑第11卷

• 发表时间: 2006
• 作者: X.Zhang;J.Jin;尾関智二(分担);T.Ozeki et al.
• 通讯作者: T.Ozeki et al.

Crystal structure of a mixed-metal β-Keggin molybdotungstosilicate, K_4[A-β-SiMo_3W_9O_<40>]-9H_2O

混合金属 β-Keggin 钼钨硅酸盐的晶体结构，K_4[A-β-SiMo_3W_9O_<40>]-9H_2O

• 发表时间: 2005
• 期刊: Polyhedron 24
• 作者: A.Ishii;T.Ozeki
• 通讯作者: T.Ozeki

The effect of carbon chain length of the diphosphine ligand on the aurophilic interaction. Synthesis and X-ray structural study for a series of Au(I) compounds with Ph2P–R–PPh2 and S-(CH2)n-py ligands

• DOI: 10.1016/j.jorganchem.2004.08.028
• 发表时间: 2005-01
• 期刊: Journal of Organometallic Chemistry
• 影响因子: 2.3
• 作者: S. Onaka;M. Yaguchi;R. Yamauchi;T. Ozeki;Mitsuhiro Ito;T. Sunahara;Yuka Sugiura;Michito Shiotsuka;Keiko Nunokawa;Makoto Horibe;Kazuya Okazaki;A. Iida;Hiroka Chiba;K. Inoue;H. Imai;K. Sako

Structure refinement of i-Al-Pd-Re quasicrystals by synchrotron radiation data

• DOI: 10.1016/j.jnoncrysol.2003.11.030
• 发表时间: 2004-03
• 期刊: Journal of Non-crystalline Solids
• 影响因子: 3.5
• 作者: A. Yamamoto;H. Takakura;T. Ozeki;A. Tsai;Y. Ohashi

Successive Phase Transitions in Crystalline State of Mesogenic Butyl 4-[2-(Perfluorooctyl)ethoxy]benzoate

介晶 4-[2-(全氟辛基)乙氧基]苯甲酸丁酯晶态的连续相变

• 发表时间: 2004
• 期刊: Chem.Lett. 33・12
• 作者: M.Maeda;M.Nagasawa;M.Tachibana;H.Kawaji;T.Atake;A.Iida;T.Ozeki;K.Hori
• 通讯作者: K.Hori