Adsorption and dehydrogenation of tetrahydroxybenzene on Cu(111)

Bebensee, Fabian; Svane, Katrine L.; Bombis, Christian; Masini, Federico; Klyatskaya, Svetlana; Besenbacher, Flemming; Rüben, Mario; Hammer, Bjørk; Linderoth, Trolle R.

doi:10.1039/c3cc45052j

Cited by 41 publications

(63 citation statements)

References 28 publications

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“…Figure 2 shows X‐ray photoelectron spectra for the network structure obtained after annealing to 440 K. The O 1s region (Figure 2 a) is dominated by a feature at a binding energy (BE) of 530.7 eV with a small shoulder at lower binding energy. From our previous study, these features can be ascribed to carbonyl and hydroxy oxygen atoms, respectively 14. The XPS data thus show that THB undergoes essentially complete dehydrogenation of all four hydroxy groups upon annealing to 440 K. The corresponding C 1s spectrum (Figure 2 b) exhibits two features with an intensity ratio of 2:1 which are ascribed to C atoms bound to oxygen (BE 285.1 eV) and hydrogen (BE 283.7 eV), in agreement with an intact ring structure 14.…”

Section: Methodsmentioning

confidence: 87%

“…From our previous study, these features can be ascribed to carbonyl and hydroxy oxygen atoms, respectively 14. The XPS data thus show that THB undergoes essentially complete dehydrogenation of all four hydroxy groups upon annealing to 440 K. The corresponding C 1s spectrum (Figure 2 b) exhibits two features with an intensity ratio of 2:1 which are ascribed to C atoms bound to oxygen (BE 285.1 eV) and hydrogen (BE 283.7 eV), in agreement with an intact ring structure 14. The formation of a fully dehydrogenated THB species is an example of on‐surface synthesis, as this species cannot be synthesized ex situ and directly deposited.…”

Section: Methodsmentioning

confidence: 87%

“…To elucidate the network structure, it is essential to know the chemical state of the constituting molecules. We previously investigated the adsorption of THB on Cu(111) and showed that the molecule undergoes dehydrogenation of two of its hydroxy groups to form dihydroxybenzoquinone (DHBQ) by annealing to 370 K 14. Figure 2 shows X‐ray photoelectron spectra for the network structure obtained after annealing to 440 K. The O 1s region (Figure 2 a) is dominated by a feature at a binding energy (BE) of 530.7 eV with a small shoulder at lower binding energy.…”

Section: Methodsmentioning

confidence: 99%

“…It is well known that Cu adatoms can be released on the Cu(111) surface by thermal activation,16 and such Cu adatoms have previously been observed to participate in metal–organic coordination networks 6b,c. 17 A precursor to the network is a close‐packed hexagonal phase of DHBQ molecules formed after annealing at 370 K 14. The periodicity of the honeycomb network (17.4 Å) is larger than twice the lattice constant of this DHBQ close‐packed hexagonal phase (7.5 Å).…”

Section: Methodsmentioning

confidence: 99%

“…Energies are reported per molecule relative to intact THB in the gas phase as shown in (a). Black bars represent DFT calculated enthalpies and red bars represent free energies at RT including the entropic contribution of desorbed H 2 and zero point energy effects 14. b) Dehydrogenated molecule adsorbed on Cu(111).…”

Section: Methodsmentioning

confidence: 99%

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A Surface Coordination Network Based on Copper Adatom Trimers

et al. 2014

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Surface coordination networks formed by coadsorption of metal atoms and organic ligands have interesting properties, for example regarding catalysis and data storage. Surface coordination networks studied to date have typically been based on single metal atom centers. The formation of a novel surface coordination network is now demonstrated that is based on network nodes in the form of clusters consisting of three Cu adatoms. The network forms by deposition of tetrahydroxybenzene (THB) on Cu(111) under UHV conditions. As shown from a combination of scanning tunneling microscopy, X-ray photoelectron spectroscopy, and density functional theory calculations, all four hydroxy groups of THB dehydrogenate upon thermal activation at 440 K. This highly reactive ligand binds to Cu adatom trimers, which are resolved by high-resolution STM. The network creates an ordered array of mono-dispersed metal clusters constituting a two-dimensional analogue of metal-organic frameworks.Metal-organic frameworks (MOFs) have emerged as an important new class of designable nanoporous materials with many potential application areas, not least within gas storage and catalysis. [1] MOFs consist of metal cations interconnected by organic linkers in a crystalline three-dimensional matrix. Motivated by sensing and other interface-related applications, thin-film MOFs have been synthesized by growing or adsorbing MOFs on surfaces. [2] The extreme case of truly two-dimensional, molecular monolayer-thick analogues of MOFs is approached from the complementary direction of surface coordination networks. [3] These structures result from advances in surface supramolecular chemistry under ultrahigh vacuum (UHV) conditions and are synthesized by coadsorbing organic ligands with metal atoms on metal singlecrystal surfaces. Early work in this direction demonstrated formation of metal-organic clusters [4] and networks [5] from coordination between carboxylates and Cu or Fe adatoms. Subsequently, many well-ordered surface coordination networks have been synthesized, [6] notably demonstrating systematic control of network pore size and symmetry from appropriate choice of ligand (size and chemical functionality), metal center, and metal substrate. [7] Bulk MOFs are based on network nodes that in many cases go beyond simple cations, for example, small metal [8] or metal-oxide clusters, such as Zn 4 O clusters in the classic MOF-5. [9] In contrast, surface coordination networks have typically been based on single metal adatom nodes or coordination nodes with two (separated) adatoms. [6c, 10] Achieving more complex network nodes [11] in surface coordination networks is an interesting prospect, as the properties of the network nodes can be key to the functionality of the MOF/surface coordination network, for example, in terms of magnetic properties [10,12] or catalytic activity. [13] Herein we use a combination of scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations to demonstrate the synt...

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Section: Methodsmentioning

confidence: 87%

Section: Methodsmentioning

confidence: 87%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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A Surface Coordination Network Based on Copper Adatom Trimers

et al. 2014

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Ein Metall‐organisches Netzwerk auf Basis von Cu‐Adatom‐ Trimeren

et al. 2014

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On‐Surface Bottom‐Up Synthesis of Azine Derivatives Displaying Strong Acceptor Behavior

et al. 2018

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On-surface synthesis is an emerging approach to obtain, in asingle step,precisely defined chemical species that cannot be obtained by other synthetic routes.The control of the electronic structure of organic/metal interfaces is crucial for defining the performance of many optoelectronic devices.A facile on-surface chemistry route has now been used to synthesize the strong electron-acceptor organic molecule quinoneazine directly on aC u(110) surface,v ia thermally activated covalent coupling of para-aminophenol precursors. The mechanism is described using ac ombination of in situ surface characterization techniques and theoretical methods. Owing to astrong surface-molecule interaction, the quinoneazine molecule accommodates 1.2 electrons at its carbonyl ends, inducing an intramolecular charge redistribution and leading to partial conjugation of the rings,conferring azo-character at the nitrogen sites.Organicheterostructuresbasedonelectronacceptor-donor organic molecules on surfaces have become strategic materials owing to their huge technological impact in fields such as organic light-emitting diodes (OLEDs), organic field effect transistors (OFETs), or solar cell devices,amongst others.In electronic devices,o rganic layers are placed on metallic surfaces for electrical contact, and the structure of the metalorganic interface enormously affects the performance.[1] In particular,s ome molecules promote charge transfer at the interface with metal electrodes owing to their donor (acceptor) nature,which may induce energy level realignment that can be exploited to tune the transport properties of the system. [1][2][3][4][5] Despite the potential impact of this approach, only af ew molecules have been shown to efficiently donate (or accept) significant charge,t his quality being related to the presence of donor (acceptor) moieties in their structures.[6] A typical example is tetracyano-p-quinodimethane (TCNQ), as trong acceptor molecule that when deposited on Cu(100) accommodates around 1.6 electrons whereby almost one electron aromatizes the central hexagonal ring and the remaining fraction of the charge is accommodated in one of the peripheral nitrogen atoms of the cyano groups.[3]On the other hand, on-surface synthesis can generate unique molecules or extended molecular architectures that have been rationally formed via alternative synthetic routes to those available through solution-based chemistry. [7,8] These surface-stabilized species can lead to compounds that are difficult or impossible to obtain via conventional synthetic procedures. [9][10][11][12] Herein, we combine both of the aforementioned features. We show that the on-surface coupling reaction of two simple and inexpensive para-aminophenol (p-Ap) molecules can be employed to form aq uinonoid-like derivative,q uinoneazine (QAz). This molecule has been theoretically proposed for organic electrodes owing to their extreme redox voltages,and it can also be employed as an intermediate in the preparation of several chemically and biologically active ...

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Adsorption and dehydrogenation of tetrahydroxybenzene on Cu(111)

Cited by 41 publications

References 28 publications

A Surface Coordination Network Based on Copper Adatom Trimers

A Surface Coordination Network Based on Copper Adatom Trimers

Ein Metall‐organisches Netzwerk auf Basis von Cu‐Adatom‐ Trimeren

On‐Surface Bottom‐Up Synthesis of Azine Derivatives Displaying Strong Acceptor Behavior

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