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

点击翻译按钮获取中文摘要

○ 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