Tribromobenzene on Cu(111): Temperature-dependent formation of halogen-bonded, organometallic, and covalent nanostructures
Tribromobenzene on Cu(111): Temperature-dependent formation of halogen-bonded, organometallic, and covalent nanostructures
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Cu(111) 上的三溴苯：卤素键合、有机金属和共价纳米结构的温度依赖性形成
DOI：
10.1063/1.4906214
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发表时间：
2015-03-14
影响因子：
4.4
通讯作者：
Gottfried, J. Michael
中科院分区：
文献类型：
--
作者：
Fan, Qitang;Wang, Tao;Gottfried, J. Michael
利用扫描隧道显微镜和超高真空 X 射线光电子能谱研究了基于 1,3,5-三溴苯 (TriBB) 的卤素键合、有机金属和共价纳米结构的温控表面辅助合成。将 TriBB 气相沉积到保持在 90 K 的 Cu(111) 表面上，导致形成蜂窝状有机单层结构的大域，该结构由带有 Br...Br 分子间键的三角形节点稳定。将有机单层退火至大约 140 K 后，形成一种新的六方密堆积结构，其中包含通过 Cu 吸附原子连接的完整 TriBB 分子。将样品进一步加热至 300 K 会导致 C-Br 键断裂，并在苯基片段之间形成 C-Cu-C 键，从而形成稳定的树枝状有机金属网络。在 TriBB 沉积过程中将 Cu(111) 的温度保持在 420 K，可以获得更大的有机金属网络岛。同时，在有机金属网络周围形成大的溴原子岛。将更延伸的有机金属网络（在 420 K 下制备）退火至 520 K 会形成支化共价有机骨架 (COF)，其包含多孔石墨烯的结构元素并被 Br 岛包围。这些有机金属网络和 COF 表现为小的树枝状和分支域，很可能是由于 Br 岛施加的空间影响。 (C) 2015 AIP 出版有限责任公司。
The temperature-controlled surface-assisted synthesis of halogen bonded, organometallic, and covalent nanostructures based on 1,3,5-tribromo-benzene (TriBB) was studied with scanning tunneling microscopy and X-ray photoemission spectroscopy in ultrahigh vacuum. Vapor deposition of TriBB onto a Cu(111) surface held at 90 K leads to the formation of large domains of a honeycomb-like organic monolayer structure stabilized by triangular nodes with Br...Br intermolecular bonds. Upon annealing the organic monolayer to similar to 140 K, a new hexagonal close-packed structure with intact TriBB molecules connected by Cu adatoms is formed. Further warming up the sample to 300 K gives rise to the scission of C-Br bonds and formation of C-Cu-C bonds between phenyl fragments such that stable dendritic organometallic networks are formed. Larger islands of organometallic networks are obtained by maintaining the temperature of Cu(111) at 420 K during deposition of TriBB. Simultaneously, large islands of Br atoms are formed around the organometallic networks. Annealing the more extended organometallic network (prepared at 420 K) to 520 K leads to the formation of a branched covalent organic framework (COF) which comprises structural elements of porous graphene and is surrounded by Br islands. These organometallic networks and COFs appear as small dendritic and branched domains, most likely due to the steric influence exerted by the Br islands. (C) 2015 AIP Publishing LLC.