Remote functionalization in surface-assisted dehalogenation by conformational mechanics: organometallic self-assembly of 3,3′,5,5′-tetrabromo-2,2′,4,4′,6,6′-hexafluorobiphenyl on Ag(111)

被引:23
|
作者
Lischka, Matthias [1 ,2 ,3 ]
Michelitsch, Georg S. [4 ,5 ]
Martsinovich, Natalia [6 ]
Eichhorn, Johanna [1 ,2 ,3 ]
Rastgoo-Lahrood, Atena [1 ,2 ,3 ]
Strunskus, Thomas [7 ]
Breuer, Rochus [8 ]
Reuter, Karsten [4 ,5 ]
Schmittel, Michael [8 ]
Lackinger, Markus [1 ,2 ,3 ,9 ]
机构
[1] Tech Univ Munich, Dept Phys, James Frank Str 1, D-85748 Garching, Germany
[2] Ctr NanoSci CENS, Schellingstr 4, D-80799 Munich, Germany
[3] Nanosyst Initiat Munich, Schellingstr 4, D-80799 Munich, Germany
[4] Tech Univ Munich, Chair Theoret Chem, Lichtenbergstr 4, D-85747 Garching, Germany
[5] Tech Univ Munich, Catalysis Res Ctr, Lichtenbergstr 4, D-85747 Garching, Germany
[6] Univ Sheffield, Dept Chem, Sheffield S3 7HF, S Yorkshire, England
[7] Christian Albrecht Univ Kiel, Inst Mat Sci Multicomponent Mat, Kaiserstr 2, D-24143 Kiel, Germany
[8] Univ Siegen, Ctr Micro & Nanochem & Engn, Organ Chem 1, Adolf Reichwein Str 2, D-57068 Siegen, Germany
[9] Deutsch Museum, Museumsinsel 1, D-80538 Munich, Germany
关键词
RAY PHOTOELECTRON-SPECTROSCOPY; GRAPHENE NANORIBBONS; ABSORPTION SPECTROSCOPY; AROMATIC-HYDROCARBONS; EXCITED-STATES; NETWORKS; COVALENT; FILMS; CORE; POLYMERIZATION;
D O I
10.1039/c8nr01987h
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Even though the surface-assisted dehalogenative coupling constitutes the most abundant protocol in on-surface synthesis, its full potential will only become visible if selectivity issues with polybrominated precursors are comprehensively understood, opening new venues for both organometallic self-assembly and on-surface polymerization. Using the 3,3,5,5-tetrabromo-2,2,4,4,6,6-hexafluorobiphenyl (Br4F6BP) at Ag(111), we demonstrate a remote site-selective functionalization at room temperature and a marked temperature difference in double- vs. quadruple activation, both phenomena caused by conformational mechanical effects of the precursor-surface ensemble. The submolecularly resolved structural characterization was achieved by Scanning Tunneling Microscopy, the chemical state was quantitatively assessed by X-ray Photoelectron Spectroscopy, and the analysis of the experimental signatures was supported through first-principles Density-Functional Theory calculations. The non-planarity of the various structures at the surface was specifically probed by additional Near Edge X-ray Absorption Fine Structure experiments. Upon progressive heating, Br4F6BP on Ag(111) shows the following unprecedented phenomena: (1) formation of regular organometallic 1D chains via remote site-selective 3,5-didebromination; (2) a marked temperature difference in double- vs. quadruple activation; (3) an organometallic self-assembly based on reversibility of C-Ag-C linkages with a thus far unknown polymorphism affording both hexagonal and rectangular 2D networks; (4) extraordinary thermal stability of the organometallic networks. Controlled covalent coupling at the previously Br-functionalized sites was not achieved for the Br4F6BP precursor, in contrast to the comparatively studied non-fluorinated analogue.
引用
收藏
页码:12035 / 12044
页数:10
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