Size-Matching Effect on Inorganic Nanosheets: Control of Distance, Alignment, and Orientation of Molecular Adsorption as a Bottom-Up Methodology for Nanomaterials

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• 作者：Shinsuke Takagi ; Tetsuya Shimada ; Yohei Ishida ; Takuya Fujimura ; Dai Masui ; Hiroshi Tachibana ; Miharu Eguchi ; Haruo Inoue
• 刊名：Langmuir
• 出版年：2013
• 出版时间：February 19, 2013
• 年：2013
• 卷：29
• 期：7
• 页码：2108-2119
• 全文大小：645K
• 年卷期：v.29,no.7(February 19, 2013)
• ISSN：1520-5827

文摘

We have been investigating complexes composed of nanolayered materials with anionic charges such as clay nanosheets and dye molecules such as cationic porphyrins. It was found that the structure of dye assembly on the layered materials can be effectively controlled by the use of electrostatic host鈥揼uest interaction. The intermolecular distance, the molecular orientation angle, the segregation/integration behavior, and the immobilization strength of the dyes can be controlled in the clay鈥揹ye complexes. The mechanism to control these structural factors has been discussed and was established as a size-matching effect. Unique photochemical reactions such as energy transfer through the use of this methodology have been examined. Almost 100% efficiency of the energy-transfer reaction was achieved in the clay鈥損orphyrin complexes as a typical example for an artificial light-harvesting system. Control of the molecular orientation angle is found to be useful in regulating the energy-transfer efficiency and in preparing photofunctional materials exhibiting solvatochromic behavior. Through our study, clay minerals turned out to serve as protein-like media to control the molecular position, modify the properties of the molecule, and provide a unique environment for chemical reactions.