Coordinatively Immobilized Monolayers on Porous Coordination Polymer Crystals
Coordinatively Immobilized Monolayers on Porous Coordination Polymer Crystals
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DOI：
10.1002/anie.201001063
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发表时间：
2010-01-01
影响因子：
16.6
通讯作者：
Kitagawa, Susumu
中科院分区：
文献类型：
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作者：
Kondo, Mio;Furukawa, Shuhei;Kitagawa, Susumu
自组装单分子膜(SAM)的形成是指化学吸附的有机分子自发地在金属或金属氧化物衬底上形成，[1]是最先进的方法，用于改变表面的界面性质，如功函数和润湿性，并赋予新的功能，如开关性质和催化反应活性。多孔性配位聚合物(PCP)或金属有机骨架(MOF)，由金属离子和桥联配体的交替排列组成[2]，可以用作基于分子的晶体底物，用于在其表面组装功能分子。这种用途允许更好地调节它们的多孔性，这对于选择性吸附、[3]多相催化、[4]和化学传感[5]等应用是有利的，因为客体分子的结合受到PCP晶体界面结构的影响。本文重点研究了在PCP表面形成类SAM单分子膜的方法，并利用配位键的平衡态在PCP晶体的靶面上制备了一种荧光有机单分子膜。已有报道表明，在SAM修饰的衬底上可以直接形成PCP。[6]在该体系中，引入到SAM分子中的配位部分在决定晶体生长方向方面起着关键作用。此外，金属前驱体与SAM之间的配位平衡对引发反应有重要影响
The formation of self-assembled monolayers (SAMs), whereby chemisorbed organic molecules spontaneously organize on metal or metal oxide substrates,[1] is the most developed method used to modify the interfacial properties of surfaces, such as work function and wettability, and to impart new functions, such as switching properties and catalytic reactivity. Porous coordination polymers (PCPs) or metal–organic frameworks (MOFs),[2] comprising an alternate arrangement of metal ions and bridging ligands, can be utilized as molecular-based crystalline substrates for the assembly of functional molecules on their surfaces. That use allows better tuning of their porous properties, which is advantageous for applications such as selective sorption,[3] heterogeneous catalysis,[4] and chemical sensing,[5] as the incorporation of guest molecules is influenced by the interfacial structures of PCP crystals. Herein we focus on the development of the methodology to form SAM-like monolayers on PCP surfaces and show the fabrication of a fluorescent organic monolayer on targeted surfaces of PCP crystals by taking advantage of the equilibrium state of coordination bonds.The relatively weak interactions of coordination bonds that dominate the construction of PCPs are also useful to hybridize PCPs with other materials. There have been reports that demonstrate the direct formation of PCPs on the SAM-modified substrates.[6] In this system, the coordination moiety introduced into the SAM molecules plays a key role in determining the orientation of the crystal growth. Moreover, the coordination equilibrium between the metal precursor and the SAM has a significant impact on the initiation of