National Synchrotron Radiation Laboratory and Collaborative Innovation Center of Suzhou Nano Science and Technology, University of Science and Technology of China , Hefei 230029, P.R. China.
ACS Nano. 2014 Jan 28;8(1):709-18. doi: 10.1021/nn405370s. Epub 2013 Dec 16.
The formation, structure, and dynamics of planar organometallic macrocycles (meta-terphenyl-Cu)n and zigzag-shaped one-dimensional organometallic polymers on a Cu(111) surface were studied with scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). Vapor deposition of 4,4″-dibromo-meta-terphenyl (DMTP) onto Cu(111) at 300 K leads to C-Br bond scission and formation of C-Cu-C bonds, which connect neighboring meta-terphenyl fragments such that room-temperature stable macrocycles and zigzag chains are formed. The chains self-assemble to form islands, which are elongated in the direction of the chains. If DMTP is deposited onto Cu(111) held at 440 K, the island size is drastically increased (>200 × 200 nm(2)). STM sequences show the formation of ordered structures through reversible scission and reformation of the C-Cu-C bonds. The cyclic organometallic species such as the hexamer (meta-terphenyl-Cu)6 may represent intermediates in the surface-confined Ullmann synthesis of hydrocarbon macrocycles such as the recently discovered hyperbenzene.
采用扫描隧道显微镜（STM）和 X 射线光电子能谱（XPS）研究了平面有机金属大环（meta-三联苯-Cu）n 和 zigzag 型一维有机金属聚合物在 Cu(111)表面上的形成、结构和动力学。在 300 K 时，将 4,4″-二溴代 meta-三联苯（DMTP）蒸气沉积到 Cu(111)上，导致 C-Br 键断裂并形成 C-Cu-C 键，这些键连接相邻的 meta-三联苯片段，从而形成室温稳定的大环和 zigzag 链。这些链自组装形成岛，这些岛在链的方向上延伸。如果将 DMTP 沉积到保持在 440 K 的 Cu(111)上，则岛的尺寸会大大增加（>200×200 nm(2)）。STM 序列显示通过 C-Cu-C 键的可逆断裂和重新形成形成有序结构。循环有机金属物种，如六聚体（meta-三联苯-Cu）6，可能代表表面受限的 Ullmann 合成烃大环（如最近发现的 hyperbenzene）中的中间体。
