Site-Selective Surface Modification of 2D Superatomic Re6Se8

被引：16

作者：

He, Shoushou ^{[1
]}

Evans, Austin M. ^{[1
]}

Meirzadeh, Elena ^{[1
]}

Han, Sae Young ^{[1
]}

Russell, Jake C. ^{[1
]}

Wiscons, Ren A. ^{[1
]}

Bartholomew, Amymarie K. ^{[1
]}

Reed, Douglas A. ^{[1
]}

Zangiabadi, Amirali ^{[1
]}

Steigerwald, Michael L. ^{[1
]}

Nuckolls, Colin ^{[1
]}

Roy, Xavier ^{[1
]}

机构：

[1] Columbia Univ, Dept Chem, New York, NY 10027 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2022年 / 144卷 / 01期

关键词：

COVALENT FUNCTIONALIZATION; LITHIUM INTERCALATION; BASIS-SET; NANOSHEETS; CLUSTERS; MOS2;

D O I：

10.1021/jacs.1c10833

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Coating two-dimensional (2D) materials with molecules bearing tunable properties imparts their surfaces with functionalities for applications in sensing, nanoelectronics, nanofabrication, and electrochemistry. Here, we report a method for the site-selective surface functionalization of 2D superatomic Re6Se8Cl2 monolayers. First, we activate bulk layered Re6Se8Cl2 by intercalating lithium and then exfoliate the intercalation compound Li2Re6Se8Cl2 in N-methylformamide (NMF). Heating the resulting solution eliminates LiCl to produce monolayer Re6Se8(NMF)(2-x) (x approximate to 0.4) as high-quality nanosheets. The unpaired electrons on each cluster in Re6Se8 (NMF)(2-x) enable covalent surface functionalization through radical-based chemistry. We demonstrate this to produce four previously unknown surface-functionalized 2D superatomic materials: Re6Se8I2, Re6Se8(SPh)(2), Re6Se8(SPhNH2)(2), and Re6Se8(SC16H33)(2). Transmission electron microscopy, chemical analysis, and vibrational spectroscopy reveal that the in-plane structure of the 2D Re6Se8 material is preserved through surface functionalization. We find that the incoming groups control the density of vacancy defects and the solubility of the 2D material. This approach will find utility in installing a broad array of chemical functionalities on the surface of 2D superatomic materials as a means to systematically tune their physical properties, chemical reactivity, and solution processability.

引用

页码：74 / 79

页数：6

共 26 条

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