Size-Matching Effect on Inorganic Nanosheets: Control of Distance, Alignment, and Orientation of Molecular Adsorption as a Bottom-Up Methodology for Nanomaterials
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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DOI：
10.1021/la3034808
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发表时间：
2013-02-19
期刊：
影响因子：
3.9
通讯作者：
Inoue, Haruo
中科院分区：
文献类型：
--
作者：
Takagi, Shinsuke;Shimada, Tetsuya;Inoue, Haruo
我们一直在研究由具有阴离子电荷的纳米层材料（如粘土纳米片）和染料分子（如阳离子卟啉）组成的复合物。研究发现，利用静电主客体相互作用可以有效地控制染料在层状材料上的组装结构。在粘土-染料复合物中，染料的分子间距离、分子取向角、分离/整合行为和固定强度可以被控制。控制这些结构因素的机制进行了讨论，并被确立为尺寸匹配效应。独特的光化学反应，如能量转移，通过使用这种方法进行了研究。作为人工捕光系统的典型实例，在粘土-卟啉复合物中实现了几乎100%的能量转移反应效率。发现分子取向角的控制在调节能量传递效率和制备表现出溶剂化变色行为的光功能材料中是有用的。通过我们的研究，粘土矿物原来是作为蛋白质样介质，以控制分子的位置，修改分子的性质，并提供一个独特的环境，化学反应。
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-guest 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-dye 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-porphyrin 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.