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

○已经制备了几种阳离子，平面钯（II），黄金（III），镍（II）和铜（II）配合物与NNN-，NC-，SS-，SS-和NNNN螯合配体的配合物已制备，这些配体已被制备，它们已经插入到GEL-V_2O_5，VOPO__4和ZR的GEL-V_2O_____4和Zr（HPO）中的插入层中。 [PDI {C_5H_4NCH_2NH（CH_2）_2 nme_2}]^+（a），[au（c_5h_5nnhc_6h_4）（s_2cnet_2）] （CH_2）_3-}; M = Cu（II）（C）和Ni（ii）（D）]复合物已与H_2O中的GET-V_2O_5 1.6H_2O的粉末反应，丙酮或EtOH提供插入化合物V_2O_5（H_2O）_2（H_2O）_2o_2O（H_2O）_5> [A] _ <0.18> __2，V_2O_3>，v_22o_3（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>。基于其层间空间（12.3-14.3 a）由粉末X射线衍射模式确定的，这些平面复合阳离子的布置与v_2o_5和vopo_4-Interlayer空间中的主机层大致平行。在V_2O_5在与nnnn-copper（II）复合物阳离子的V_2O_5中，c c c c c c c c c c c c c c c cym c c cyper（ii）离子由v_2o_5晶格的氧原子协调，表明宾客相互作用。另一方面，在Zr（HPO_4）的层间空间（16.7 a）中，_2（H_2O）_ <0.5> [C] _ <0.4>宾客金属 - 复合分子被降低到宿主表的垂直方向。宿主晶格和宾客金属复合物分子之间没有特殊的相互作用。○与分子变形有关的铁络合物的自旋分叉现象，例如对称呼吸和三角形扭转。那就可以用作对分子环境的敏感探针。粘土宿主化合物NATSM（氟化钠云母）的层间效果已通过磁敏感性和 ^<57> femossbauer光谱术为铁配合物进行了研讨会。所检查的来宾复合物分子为[Fe^<ii>（AMP）_3]^<2+>（AMP = 2-氨基 - 甲基吡啶），[Fe^<iii>（ACPA）_2]^+（hacpa = n- = n-（hacpa = n-（1-乙酰基 - 2-乙酰基 - 2-丙糖基）-2-丙二酰基_2- pyridylidylmethylamine和[feirien sallien and II III>（[+]+ [+ II>（[feien）+ [+ II>]+ [> II> II>] <] （h_2sal_2trien = n，n'-二甲基环乙烯乙烯胺）。已经观察到了在intewrayerer空间中高自旋 - 低自旋能隙的显着降低。较少的