Ullmann Coupling Reactions on Ag(111) and Ag(110); Substrate Influence on the Formation of Covalently Coupled Products and Intermediate Metal-Organic Structures.
Ullmann Coupling Reactions on Ag(111) and Ag(110); Substrate Influence on the Formation of Covalently Coupled Products and Intermediate Metal-Organic Structures.
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DOI：
10.1038/s41598-017-13315-1
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发表时间：
2017-11-06
影响因子：
4.6
通讯作者：
Saywell A
中科院分区：
文献类型：
--
作者：
Judd CJ;Haddow SL;Champness NR;Saywell A
已知基于Ullmann偶联的表面上反应在硬币-金属基底（例如Au、Ag、Cu）上进行，其中表面的化学性质强烈影响反应进程。此外，表面的形貌可能会影响反应物的局部吸附几何形状以及中间和最终结构。本文研究了银的两种不同表面晶面Ag（111）和Ag（110）对Ullmann型偶联反应中有机金属结构和共价结构形成的影响。4，4”-二碘间三联苯分子在Ag（111）或Ag（110）表面上的沉积导致C-I键断裂，随后形成由配位键连接到Ag吸附原子的分子组成的有机金属锯齿形结构。通过退火每个表面形成共价偶联的产物，导致Ag原子的去除和共价键合的锯齿形聚（间苯）结构的形成。退火前后每个表面上分子吸附模型的比较表明，在Ag（111）上，结构通过旋转和键的伸长重新排列，以便与表面相称，而对于Ag（110）表面，中间和最终状态的吸附几何形状的相似性意味着不需要旋转。
On-surface reactions based on Ullmann coupling are known to proceed on coinage-metal substrates (e.g. Au, Ag, Cu), with the chemistry of the surface strongly influencing the reaction progression. In addition, the topography of the surface may be expected to affect the local adsorption geometry of the reactants as well as the intermediate and final structures. Here, we investigate the effect of two different surface facets of silver, Ag(111) and Ag(110) on the formation of organometallic and covalent structures for Ullmann-type coupling reactions. Deposition of 4,4”-diiodo-m-terphenyl molecules onto either Ag(111) or Ag(110) surfaces leads to the scission of C-I bonds followed by the formation of organometallic zigzag structures, consisting of molecules connected by coordination bonds to Ag adatoms. The covalently coupled product is formed by annealing each surface, leading to the removal of Ag atoms and the formation of covalently bonded zigzag poly(m-phenylene) structures. Comparisons of the adsorption model of molecules on each surface before and after annealing reveal that on Ag(111), structures rearrange by rotation and elongation of bonds in order to become commensurate with the surface, whereas for the Ag(110) surface, the similarity in adsorption geometry of the intermediate and final states means that no rotation is required.
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