標題: Porous Self-Assembled Molecular Networks as Templates for Chiral-Position-Controlled Chemical Functionalization of Graphitic Surfaces
作者: Tahara, Kazukuni
Kubo, Yuki
Hashimoto, Shingo
Ishikawa, Toru
Kaneko, Hiromasa
Brown, Anton
Hirsch, Brandon E.
De Feyter, Steven
Tobe, Yoshito
應用化學系
Department of Applied Chemistry
公開日期: 22-Apr-2020
摘要: Controlled covalent functionalization of graphitic surfaces with molecular scale precision is crucial for tailored modulation of the chemical and physical properties of carbon materials. We herein present that porous self-assembled molecular networks (SAMNs) act as nanometer scale template for the covalent electrochemical functionalization of graphite using an aryldiazonium salt. Hexagonally aligned achiral grafted species with lateral periodicity of 2.3, 2.7, and 3.0 nm were achieved utilizing SAMNs having different pore-to-pore distances. The unit cell vectors of the grafted pattern match those of the SAMN. After the covalent grafting, the template SAMNs can be removed by simple washing with a common organic solvent. We briefly discuss the mechanism of the observed pattern transfer. The unit cell vectors of the grafted pattern align along nonsymmetry axes of graphite, leading to mirror image grafted domains, in accordance with the domain-specific chirality of the template. In the case in which a homochiral building block is used for SAMN formation, one of the 2D mirror image grafted patterns is canceled. This is the first example of a nearly crystalline one-sided or supratopic covalent chemical functionalization. In addition, the positional control imposed by the SAMN renders the functionalized surface (homo)chiral reaching a novel level of control for the functionalization of carbon surfaces, including surface-supported graphene.
URI: http://dx.doi.org/10.1021/jacs.0c02979
http://hdl.handle.net/11536/154448
ISSN: 0002-7863
DOI: 10.1021/jacs.0c02979
期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume: 142
Issue: 16
起始頁: 7699
結束頁: 7708
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