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

• 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
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11640564/
• 关键词: Intercalation; Vanadium oxide; Oxovanadium phosphate; Zirconium phosphate; Palladium complex; Nickel complex; Copper complex; Spin-crossover complex; 金錯体; 白金錯体; ピリジル錯体

○ 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

○合成了NNN-、NC-、SS-和NNNN-四种阳离子平面钯（II）、金（III）、镍（II）和铜（II）配合物，并将其插层到凝胶-V_2 O_5、VOPO_4和Zr（HPO_4）_2主体化合物的层间。[PdI{C_5H_4NCH_2NH（CH_2）_2 NMe_2}]^+（A），[Au（C_5H_5NNHC_6H_4）（S_2CNEt_2）]^+（B），和[M（cyclam）]^&lt;2+&gt; [cyclam={-NH（CH_2）_2 NH（CH_2）_3-} ; M=Cu（II）（C）和Ni（II）（D）]配合物与get-V_2 O_5 1.6H_2 O粉末在水、丙酮或乙醇中反应，得到插层化合物V_2O_5（H_2O）_<0.5>[A]_<0.18>、V_2O_5（H_2O）_[B]_<0.04>、V_2O_5（H_2O）_<0.5>[C]_<0.15>和V_2O_5（H_2O）_<0.5>[D]_<0.14>。根据X射线粉末衍射测定的层间距（12.3- 14.3A），这些平面配合物阳离子在V_2O_5-和VOPO_4-层间距中近似平行于基质层排列。在V_2O_5与NNNN-Cu（II）络合阳离子形成的层间化合物中， ...更多信息 Cu（Ⅱ）离子与V_2O_5晶格中的氧原子配位，表明存在主客体相互作用。而在Zr（HPO_4）_2（H_2O）_ [C]_的层间空间（16.7）中<0.5>，<0.4>客体金属络合物分子向主体片的垂直方向倾斜。主体晶格与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的对称呼吸和三角扭转等形变。因此，它们可以作为分子环境的敏感探针。用磁化率和穆斯堡尔谱研究了粘土基质化合物NaTSM（sodium云母）对铁配合物的层间限制效应<57>。所研究的客体配合物分子为[Fe^<II>（amp）_3]^&lt;2+&gt;（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 '-二亚丙基三亚乙基四胺）。观察到层间空间的高自旋-低自旋能隙显著减小。少

项目成果

中野元裕: "Spin-crossover Phenomena of Iron Complexes in the NaTSM Intercalation Compounds"Mol.Cryst.Liq.Cryst.. (印刷中).

Motohiro Nakano：“NaTSM 插层化合物中铁配合物的自旋交叉现象”Mol.Cryst.Liq.Cryst..（出版中）。