Organic-inorganic Hybrid Systems Research Articles

水素結合における構造物性と機能 水素結合と電子状態

In this report, the cooperation of electron and proton in organic-inorganic hybrid systems is discussed.Particularly, the experimental results of the X-ray diffraction measurements on the 1-D metallic charge-transfer crystal of [Pd (H2-xEDAG) (HEDAG) ] TCNQ (EDAG=ethylenediaminoglyoxime, x=ca. 0.7) were focused. Below the metal-insulator (M-I) phase transition (180 K), commensurate superlattice reflections were observed with a period of c*/2, c*/3, and c*/12 along the 1-D axis, c. The full X-ray diffraction analyses of temperature-dependent reflections ignoring the superlattice spots show remarkable anomalies of the temperature factors below 180 K for several atoms which associate with the intermolecular H-bonds between donor-molecules. This is a result of cooperation between the order-disorder transition of the 1-D H-bond intermolecular superlattice and the M-I transition of the 1-D electronic state in TCNQ acceptor stacks. These experimental results support a model of purely 1-D metallic hole-conduction introduced by partial deprotonation of H-bonds in the ligands of [Pd (H2-xEDAG) (HEDAG) ] .

High-temperature spectral hole burning for organic—inorganic hybrid systems: porphyrin derivative-doped alumina gels prepared by a sol—gel method

We prepared sol—gel glasses doped with organic molecules to achieve high-temperature hole burning (HTHB) with high efficiency. We used 5,10,15,20-tetra(4-carboxyphenyl)-21H,23H-porphine tetrasodium (TPPC(Na)) and mesoporphyrin IX disodium (MP(Na)) as organic dyes and Al 2O 3 as an inorganic matrix. We could burn holes at 20 K with a quantum yield of 2.8 × 10 −3 for MP(Na)/Al 2O 3 and 5.4 × 10 −4 for TPPC(Na)/Al 2O 3. The organic dye/Al 2O 3 system has a smaller temperature dependence of the Debye—Waller factor than dye/polymer systems. We could burn holes even at 132 K, which is one of the highest hole burning temperatures among the free-base porphyrin systems and the highest among the organic dye/Al 2O 3 systems.

Electron-Proton Co-operation in l-D d-π Electronic State-Basic Study of Protono-Electronics-

Abstract The electron-proton co-operation in organic-inorganic hybrid systems, [Pd(H2-x EDAG) (HEDAG)] · TCNQ and [Pt(H2-x DAG) (HDAG)] · TCNQ complexes, leads to two different types of the metal-insulator transition, which originate in the instability of the 1-D π electronic state of the TCNQ stacks. Here, HDAG or HEDAG stands for hydro-or hydroethylene-diaminoglyoxime. Their driving forces are attributable to freezing of the fluctuation of protons in the interchain H-bonds and the charge transfer from the [Pt(H2-x DAG) (HDAG)] metal complex to TCNQ stacks, respectively.

Hybrid Organic-Inorganic Systems Derived from Organotin Nanobuilding Blocks

A new synthesis of the macro-cation [(BuSn){sub 12}O{sub 14}(OH){sub 6}]{sup 2+} is described from commercially available and easy to handle BuSnO(OH) and p-toluene sulfonic acid. A crystalline compound, [(BuSn){sub 12}O{sub 14}(OH){sub 6}] (O{sub 3}SC{sub 6}H{sub 4}CH{sub 3}){sub 2}{center_dot}C{sub 4}H{sub 8}O{sub 2}, is obtained. It can react with tetramethylammonium hydroxide to yield the more versatile composition: [(BuSn){sub 12}O{sub 14}(OH){sub 6}](OH){sub 2}. The macro-cations are then used as nanobuilding blocks and assembled in rosary-like structures by carboxy-terminated poly(ethyleneglycol). The resulting system can be pictured as hybrid organic-inorganic alternated block co-polymers. Characterizations were performed with {sup 119}Sn NMR (solution and solid state), {sup 13}C CP-MAS NMR and FT-IR.

Structure-property behaviour of hybrid materials incorporating tetraethoxysilane with multifunctional poly(tetramethylene oxide)

Polytetramethylene oxide based polyurethane oligomers with multiple triethoxysilane groups have been successfully incorporated into a TEOS based silicate network. It is observed that the incorporation of these oligomeric compounds was enhanced by the presence of additional functional groups along their backbone. The materials produced showed significant improvement in both tensile modulus and strength over previous organic-inorganic hybrid systems. As the number of functional groups per molecule increased, the stiffness of the material increased and the oligomeric T g shifted to higher temperatures. Also, the SAXS correlation distance decreased systematically. A schematic model suggested previously can still be used to interpret these results. Other effects of TEOS content and ageing are also reported and discussed.