Preparation of new inorganic superlattices by two-dimensional ordering of metal orbitals

金属轨道二维有序制备新型无机超晶格

• 批准号: 06555187
• 负责人: KUNITAKE Toyoki
• 金额: $ 10.82万
• 依托单位: KYUSHU UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Developmental Scientific Research (B)
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-06555187/
• 关键词: Photo-induced growth; Cast film; ESR spectroscopy; Cyano-bridged clusters; 量子効果; 単分子膜; キャストフィルム; 分子鋳型; 無機超薄膜; 低次元シアノ架橋錯体; 酸化モリブデン

The present study aimed at precise structural control of various inorganic clusters by using cast films of bilayr membranes of synthetic amphiphiles. Major accomplishments are as follows.1) A new bilayr with dicationic viologen head group was synthesized to enhance the density of inorganic guest molecules incorporated into the interlayr.2) Ni (CN)_4, Au (CN)_4, Pt (CN)_4, MoS_4, were introduced into the layr by ion exchange, and then Cu (II) ion was introduced by immersion. Infrared spectroscopy indicated the formation of cyano-bridged clusters in the case of Ni-Cu and Pt-Cu films. ESR spectroscopy of these two films display remarkable anisotropies which suggest that a Cu (II) d orbital is placed parallel to the film layr with regular spin ordering similar to that of crystals.3) The MoS_4/Cu (II) complex that was prepared by sequential synthesis on the cast film template does not give ESR signals of Cu (II) itself in consistence with the presumed structure. Therefore, cluster formation that accompany redox reaction of the precursor ion is achieved.4) Photo-induced growth of a Fe (II) -Fe (III) mixed valence complex was found by using the monolayr template at the air-water interface.

本研究的目的是通过使用合成的两亲物的双层膜的流延膜的各种无机团簇的精确结构控制。主要成果如下：1）合成了一种新的双阳离子紫精头基双层膜，以提高无机客体分子嵌入层间的密度; 2）通过离子交换法引入Ni（CN）_4、Au（CN）_4、Pt（CN）_4、MoS_4，再通过浸渍法引入Cu（II）离子。红外光谱表明，形成的氰基桥接团簇的情况下，Ni-Cu和Pt-Cu膜。这两种膜的ESR谱都显示出明显的各向异性，表明Cu（II）d轨道平行于膜层，具有与晶体相似的规则自旋有序。3）在铸膜模板上顺序合成的MoS_4/Cu（II）配合物没有给出与推测结构一致的Cu（II）本身的ESR信号。4）利用单层模板在空气-水界面上发现了Fe（II）-Fe（III）混合价络合物的光诱导生长。

项目成果

N.Kimizuka et.al.: "Mesoscopic Supramolecular Assembly of a ′Janus′Molecule and a Melamine Derivative via Complementary Hydrogen Bonds" J.Chem.Soc.Chem.Commun,. 2103-2104 (1995)

N.Kimizuka 等人：“Janus”分子和三聚氰胺衍生物通过互补氢键的介观超分子组装”J.Chem.Soc.Chem.Commun，2103-2104 (1995)。

Munetoshi Isayama: "Self-Supporting Films of Clay Minerals and Metal Oxide:Molecular Ceramics" Advanced Ceramics. 6. 77-78 (1994)

Munetoshi Isayama：“粘土矿物和金属氧化物的自支撑薄膜：分子陶瓷”先进陶瓷。

T.Kunitake et.al.: "Formation of a Novel CdS Cluster in an Organic Multibilayar Template : A Case of an Organic/Inorganic Superlattice" T.Phys.Chem. 99. 3736-3742 (1995)

T.Kunitake 等人：“有机多层模板中新型 CdS 簇的形成：有机/无机超晶格的案例”T.Phys.Chem。

T.Kunitake et.al.: "Formation of a Novel CdS Cluster in an Organic Multibilayer Template:A Case of an Organic/lnorganic Superlattice" J.Phys.chem. 99. 3736-3742 (1995)

T.Kunitake 等人：“有机多层模板中新型 CdS 簇的形成：有机/无机超晶格的案例”J.Phys.chem。

T.Kunitake et.al.: "Assembly of Multicomponent Protein Films by Means of Electrostatic Layer-by-Layer Adsorption" J.Am.Chem.Soc.117. 6117-6123 (1995)

T.Kunitake 等人：“通过静电逐层吸附组装多组分蛋白质膜”J.Am.Chem.Soc.117。