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

基本信息

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

项目摘要

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

该研究项目的目的是将多氧金属元素与过渡金属离子合成，分析其晶体结构，然后检查其结构特定的物理特性。首先，研究了[Cu_2（OH）_2（OH_2）_6] [Cu_2（OH__2）_8] [V_ <10> O_ <28>] -4（CH_3）_2CO，首先研究了由研究者合成和表征的。该化合物在[V_ <10> O_ <28>]^<6->核心的两侧有两对Cu^<2+>阳离子，分别分别为2.89Å和3.37Å。这些对的不配对电子未耦合，每个Cu^<2+>原子都可以作为一个独立的自旋中心。其次，合成了[V_ <10> o_ <28>]^<6->的双盐，并合成了cu^<2+>和nh_4^+，k^+或rb^+的双盐，并确定了其晶体结构。这些晶体，水分子与阳离子的坐标支持[V_ <10> O_ <28>]^<6->核通过氢键在[V_ <10> o_ <28>]^核心上稳定下来，并稳定了单质体的物种，[hv…更多_ <10> _O _O <28>]^<5-5->。在这些晶体中，首先明确确定质子在单质脱叶酸阴离子上的精确位置。另外，[siw_ <11> o_ <39>]^<8->用Na^+和鸟嘌呤阳离子结晶的结构确定表明，该化合物表现出[siw_ <11> o_ <11> o_ <39>]^<8-> na^+阳离子链接的新型螺钉结构，尽管过渡金属未融合到该化合物中。它的结构表明它可能显示出非线性光学特性，从而辐照800 nm波长的脉冲激光，从而观察到第二次谐波生成。与这些研究同时，研究者在两个同步器设施上安装和升级了衍射仪：高能量加速器研究组织的Spring-8和光子工厂。这些努力证明了上述NLO活性有机硅晶体的精确结构分析，以及分子生长和混合价值钼巨型群的分子生长和分子间凝结的结构阐明，其纳米大小的环形。较少的