Synthesis of Two-Dimensional Analogues of Copolymers by Site-to-Site Transmetalation of Organometallic Monolayer Sheets

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• 作者：Zhikun Zheng ; Lothar Opilik ; Florian Schiffmann ; Wei Liu ; Giacomo Bergamini ; Paola Ceroni ; Lay-Theng Lee ; Andri Sch眉tz ; Junji Sakamoto ; Renato Zenobi ; Joost VandeVondele ; A. Dieter Schl眉ter
• 刊名：Journal of the American Chemical Society
• 出版年：2014
• 出版时间：April 23, 2014
• 年：2014
• 卷：136
• 期：16
• 页码：6103-6110
• 全文大小：421K
• 年卷期：v.136,no.16(April 23, 2014)
• ISSN：1520-5126

文摘

Monolayer sheets have gained attention due to the unique properties derived from their two-dimensional structure. One of the key challenges in sheet modification/synthesis is to exchange integral parts while keeping them intact. We describe site-to-site transmetalation of Zn²⁺ in the netpoints of cm²-sized, metal鈥搊rganic sheets by Fe²⁺, Co²⁺, and Pb²⁺. This novel transformation was done both randomly and at predetermined patterns defined by photolithography to create monolayer sheets composed of different netpoints. All transmetalated sheets are mechanically strong enough to be spanned over 20 脳 20 渭m² sized holes. Density functional theory calculations provide both a model for the molecular structure of an Fe²⁺-based sheet and first insights into how transmetalation proceeds. Such transmetalated sheets with random and patterned netpoints can be considered as two-dimensional analogues of linear copolymers. Their nanoscale synthesis presents an advance in monolayer/polymer chemistry with applications in fields such as surface coating, molecular electronics, device fabrication, imaging, and sensing.