Single Layer of Polymeric Fe-Phthalocyanine: An Organometallic Sheet on Metal and Thin Insulating Film

Abel, Markus; Clair, Sylvain; Ourdjini, Oualid; Mossoyan, M.; Porte, L.

doi:10.1021/ja108628r

Cited by 383 publications

(346 citation statements)

References 36 publications

(60 reference statements)

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“…2). Recently, the chemical structure of the polymer formed by this reaction was confirmed by the scanning tunneling microscopy (STM) for the case of Fe [5]. However, only nano-scale samples were achieved, while the experimental set-up was quite complex (ultra-high-vacuum conditions and atomically clean surfaces).…”

Section: Introductionmentioning

confidence: 99%

Synthesis and structure of high-quality films of copper polyphthalocyanine – 2D conductive polymer

Sedlovets

Shuvalov

Vishnevskiy

et al. 2013

Materials Research Bulletin

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ABSTRACT:We propose an experimental approach, by which thin films of copper polyphthalocyanine (CuPPC) can be directly synthesized in a chemical vapor deposition (CVD) set-up at mild temperature (420 °C). High polymerization degree and high crystallinity of the films was confirmed by TEM, FTIR and UV-VIS studies; the stacking structure of CuPPC layers was determined, inter-layer spacing was estimated from XRD and TEM electron-diffraction. Quantum-chemical study performed providing support for experimental structure determination and yielding information on the electronic structure.

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Section: Introductionmentioning

confidence: 99%

Synthesis and structure of high-quality films of copper polyphthalocyanine – 2D conductive polymer

Sedlovets

Shuvalov

Vishnevskiy

et al. 2013

Materials Research Bulletin

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“…Thus, it is a timely issue to explore acetylenic coupling at interfaces, and recent studies using a sequential protocol with monolayer self-assembly followed by a crosslinking step provided encouraging results 11 . Pursuing a different vein, there is the prospective research domain dealing with on-surface covalent reactions under ultrahigh vacuum (UHV) conditions on clean metal surfaces to realize novel functional nano-architectures and networks [12][13][14][15][16][17][18][19] . However, many of the employed protocols imply appreciable activation barriers or rely on the enabling character of a set of leaving groups.…”

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confidence: 99%

Homo-coupling of terminal alkynes on a noble metal surface

et al. 2012

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The covalent linking of acetylenes presents an important route for the fabrication of novel carbon-based scaffolds and two-dimensional materials distinct from graphene. To date few attempts have been reported to implement this strategy at well-defined interfaces or monolayer templates. Here we demonstrate through real space direct visualization and manipulation in combination with X-ray photoelectron spectroscopy and density functional theory calculations the Ag surface-mediated terminal alkyne C sp À H bond activation and concomitant homo-coupling in a process formally reminiscent of the classical Glaser-Hay type reaction. The alkyne homo-coupling takes place on the Ag(111) noble metal surface in ultrahigh vacuum under soft conditions in the absence of conventionally used transition metal catalysts and with volatile H 2 as the only by-product. With the employed multitopic ethynyl species, we demonstrate a hierarchic reaction pathway that affords discrete compounds or polymeric networks featuring a conjugated backbone. This presents a new approach towards on-surface covalent chemistry and the realization of two-dimensional carbon-rich or allcarbon polymers.

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“…29−31 These achievements have been reviewed in refs 6 and 8, focusing on the relevant experimental and theoretical studies to date, respectively. Despite the considerable progress achieved on metal surfaces, comparatively fewer studies of synthesis on insulating substrates are available in the literature, including reactions on bulk surfaces through Ullmann-type processes, 3,6,19,32 photochemical initiation, 20 and reactions on insulating thin films 18 (see also ref 6 and references therein). Several factors make on-surface syntheses on insulators rather challenging.…”

Section: Introductionmentioning

confidence: 99%

Mechanisms of Covalent Dimerization on a Bulk Insulating Surface

Guo

Wang

Kittelmann³

et al. 2017

J. Phys. Chem. C

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Combining density functional theory and highresolution NC-AFM experiments, we have studied the onsurface reaction mechanisms responsible for the covalent dimerization of 4-iodobenzoic acid (IBA) organic molecules on the calcite (10.4) insulating surface. When annealed at 580 K, the molecules assemble in one-dimensional chains of covalently bound dimers. The chains have a unique orientation and result from a complex set of processes, including a nominally rather costly double dehalogenation reaction followed by dimerization. First, focusing on the latter two processes and using the nudged elastic band method, we analyze a number of possible mechanisms involving one and two molecules, and we isolate the key aspects facilitating the reaction on calcite. Second, we find that the insulating surface plays an active role as a catalyst by identifying two relevant processes: one exhibiting an intermediate state of chemisorbed molecules after independent dehalogenations and a second, highly nontrivial exothermic reaction channel in which two iodine atoms "cooperate" to minimize the cost of their individual detachment from the molecules. Both processes have dramatically reduced energy barriers compared to all other mechanisms analyzed. The knowledge of the formation mechanisms of a covalent assembly on insulators represents an important step toward the realization and control of structures that combine the robustness of covalent architectures with their electronic decoupling from the insulating substrate. This step has potentially important technological applications in nano-and molecular electronics.

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Single Layer of Polymeric Fe-Phthalocyanine: An Organometallic Sheet on Metal and Thin Insulating Film

Cited by 383 publications

References 36 publications

Synthesis and structure of high-quality films of copper polyphthalocyanine – 2D conductive polymer

Synthesis and structure of high-quality films of copper polyphthalocyanine – 2D conductive polymer

Homo-coupling of terminal alkynes on a noble metal surface

Mechanisms of Covalent Dimerization on a Bulk Insulating Surface

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