Formation of New Interlayer Spaces constructed with Metal Ions and Intercalation of Metal Complexes

由金属离子构建的新层间空间的形成和金属配合物的插层

基本信息

批准号：
11640564
负责人：
MATSUBAYASHI Gen-etsu
金额：
$ 1.6万
依托单位：
Osaka University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1999
资助国家：
日本
起止时间：
1999 至 2000
项目状态：
已结题

项目摘要

○ Several cationic, planar palladium (II), gold (III), nickel (II) and copper (II) complexes with NNN-, NC-, SS-, and NNNN chelate ligands have been prepared, which have been intercalated into interlayer spaces of gel-V_2O_5, VOPO_4 and Zr (HPO_4)_2 host compounds. [PdI {C_5H_4NCH_2NH (CH_2)_2 NMe_2}]^+ (A), [Au(C_5H_5NNHC_6H_4)(S_2CNEt_2)]^+ (B), and [M (cyclam)]^<2+> [cyclam={-NH (CH_2)_2 NH (CH_2)_3-} ; M=Cu (II)(C) and Ni (II)(D)] complexes have been reacted with powders of get-V_2O_5 1.6H_2O in H_2O, acetone or EtOH to afford intercalation compounds V_2O_5(H_2O)_<0.5>[A]_<0.18>, V_2O_5 (H_2O)_<1.3^-> [B]_<0.04>, V_2O_5 (H_2O)_<0.5>[C]_<0.15>, and V_2O_5(H_2O)_<0.5>[D]_<0.14>. Based on their interlayer spaces (12.3-14.3 A) determined by powder X-ray diffraction patterns, these planar complex cations are arranged approximately parallel to the host layers in the of V_2O_5-and VOPO_4-interlayer spaces. In the V_2O_5 intercalation compound with the NNNN-copper (II) complex cation the c … More opper (II) ion is coordinated by the oxygen atom of the V_2O_5 lattice, indicating a guest-host interaction. On the other hand, in the interlayer space (16.7 A) of Zr (HPO_4)_2(H_2O)_<0.5>[C]_<0.4> the guest metal-complex molecules are declined to the perpenducular direction of the host sheet. There is no particular interaction between the host lattice and guest metal-complex molecules.○ The spin-crossover phenomena of iron complexes accompany with molecular deformations such as symmetric breathing and trigonal torsion. Thus, they can serve as a sensitive probe to molecular surroundings. A confinement effect into interlayer spaces of a clay host compound, NaTSM (sodium fluorotetrasilicic mica), have been studied for iron complexes by magnetic susceptibility and ^<57>FeMossbauer spectroscopy. Guest complex molecules examined are [Fe^<II> (amp)_3]^<2+> (amp=2-amino-methylpyridine), [Fe^<III> (acpa)_2]^+ (Hacpa=N-(1-acetyl-2-propylidene)-2-pyridylmethylamine), and[Fe^<III> (sal_2trien)]^+ (H_2sal_2trien=N,N'-disalicylidenetri-ethylenetetramine). A remarkable reduction of the high spin-low spin energy gap in the intewrlayer space has been observed. Less

○ 制备了几种带有NNN-、NC-、SS-和NNNN螯合配体的阳离子、平面钯(II)、金(III)、镍(II)和铜(II)配合物，这些配合物已插入层间空间凝胶-V_2O_5、VOPO_4 和 Zr (HPO_4)_2 主体化合物 [PdI {C_5H_4NCH_2NH]。 (CH_2)_2 NMe_2}]^+ (A)、[Au(C_5H_5NNHC_6H_4)(S_2CNEt_2)]^+ (B) 和 [M (cyclam)]^<2+> [cyclam={-NH (CH_2)_2 NH (CH_2)_3-} ; M=Cu (II)(C) 和 Ni (II)(D)] 络合物已反应与 get-V_2O_5 1.6H_2O 粉末在 H_2O、丙酮或 EtOH 中反应，得到插层化合物 V_2O_5(H_2O)_<0.5>[A]_<0.18>、V_2O_5 (H_2O)_<1.3^-> [B]_<0.04 >、V_2O_5 (H_2O)_<0.5>[C]_<0.15>和V_2O_5(H_2O)_<0.5>[D]_<0.14>基于通过粉末X射线衍射测定的它们的层间距(12.3-14.3A)。在图案中，这些平面复合阳离子大致平行于 V_2O_5 和 VOPO_4 层间空间中的主体层排列。在具有 NNNN-铜 (II) 络合物阳离子的 V_2O_5 插层化合物中，铜 (II) 离子与 V_2O_5 晶格的氧原子配位，表明在层间存在客体相互作用。 Zr (HPO_4)_2(H_2O)_<0.5>[C]_<0.4> 客体空间 (16.7 A)金属配合物分子向主片的垂直方向倾斜。主晶格和客体金属配合物分子之间没有特殊的相互作用。○铁配合物的自旋交叉现象伴随着分子变形，例如对称呼吸和三角变形。因此，它们可以作为粘土主体化合物 NaTSM（氟四硅云母钠）层间空间的敏感探针。通过磁化率和 ^<57>FeMossbauer 光谱研究了铁配合物，检测的客体配合物分子为 [Fe^<II> (amp)_3]^<2+> (amp=2-氨基甲基吡啶)、[Fe^< III> (acpa)_2]^+ (Hacpa=N-(1-乙酰基-2-亚丙基)-2-吡啶基甲胺)，和[Fe^<III> (sal_2trien)]^+ (H_2sal_2trien=N,N'-二水杨基三亚乙基四胺) 已观察到层间空间的高自旋-低自旋能隙显着减小。