2000 Fiscal Year Final Research Report Summary
Formation of New Interlayer Spaces constructed with Metal Ions and Intercalation of Metal Complexes
| Project/Area Number |
11640564
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Inorganic chemistry
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| Research Institution | Osaka University |
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Principal Investigator |
MATSUBAYASHI Gen-etsu Osaka University, Graduate School of Engineering, Professor, 大学院・工学研究科, 教授 (90029182)
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| Project Period (FY) |
1999 – 2000
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| Keywords | Intercalation / Vanadium oxide / Oxovanadium phosphate / Zirconium phosphate / Palladium complex / Nickel complex / Copper complex / Spin-crossover complex |
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| Research Abstract |
○ 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
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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
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