Controlled growth of ordered monolayers of N-heterocyclic carbenes on silicon

Franz, M.; Chandola, S.; Koy, Maximilian; Zielinski, Robert; Aldahhak, Hazem; Das, Mowpriya; Freitag, Matthias; Gerstmann, Uwe; Liebig, Denise; Hoffmann, Adrian Karl; Rosin, Maximilian; Schmidt, Wolf Gero; Hogan, Conor; Glorius, Frank; Esser, N.; Dähne, M.

doi:10.1038/s41557-021-00721-2

Cited by 48 publications

(77 citation statements)

References 58 publications

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“…Since the seminal report by Arduengo et al., [1] N‐heterocyclic carbenes (NHCs) have fostered considerable interest in catalysis, [2–4] as ligands for p‐block elements [5] and transition metals, [6] thanks to their unique properties [7, 8] . Owing to the strong σ‐donating ability and the high tunability of the side‐groups, manifold applications dealing with the functionalization of surfaces [9–13] and nanoparticles [14–21] have been reported [22–24] . The even stronger propensity towards σ‐donation of cyclic (alkyl)(amino) carbenes (CAAC) [25, 26] has been highlighted both in catalytic applications [27] and in pioneering on‐surface reactivity studies by Johnson and co‐workers, [28] but little is known about the fundamental behavior of such entities on metal surfaces [29] .…”

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confidence: 99%

Reversible Self‐Assembly of an N‐Heterocyclic Carbene on Metal Surfaces

et al. 2022

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Self‐assembly of cyclohexyl cyclic (alkyl)(amino)carbenes (cyCAAC) can be realized and reversibly switched from a close‐packed trimer phase to a chainlike dimer phase, enabled by the ring‐flip of the cyclohexyl wingtip. Multiple methods including scanning tunneling microscopy (STM), X‐ray photoelectron spectroscopy (XPS) and density functional theory (DFT) calculations identified a distinct isomer (axial or equatorial chair conformer) in each phase, and consequently support the conclusion regarding the determination of molecular surface geometry on the self‐assembly of cyCAAC. Moreover, various substrates such as Ag (111) and Cu (111) are tested to elucidate the importance of cyCAAC‐surface interactions on cyCAAC based nanopatterns. These investigations of patterned surfaces prompted a deep understanding of cyCAAC binding mode, surface geometry and reversible self‐assembly, which are of paramount significance in the areas of catalysis, biosensor design and surface functionalization.

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Section: Introductionmentioning

confidence: 99%

Reversible Self‐Assembly of an N‐Heterocyclic Carbene on Metal Surfaces

et al. 2022

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“…In the field of semiconductors silicon is the most relevant element and the precise modification and functionalization of silicon surfaces is a research area of high interest. 1 Reports on reconstructed silicon(100)2 × 1 surfaces show, that the first layer is composed of a pair of trigonal pyramidal and trigonal planar silicon atoms which is called “buckled dimer” (Fig. 1, Top).…”

Section: Introductionmentioning

confidence: 99%

A strongly twisted SiSi bond with resemblance to a buckled dimer in an unexpected isomer of hexasilabenzene

2022

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“…N-heterocyclic carbene (NHC) ligands’ strong metal-carbon bonds and highly tunable structures enable numerous applications, including organometallic catalysis, − electronics, supramolecular chemistry, metal–organic frameworks, and medicinal chemistry . To add to this considerable collection, NHCs were recently shown to form robust self-assembled monolayers (SAMs) − stable under electrochemical cycling, high temperatures, − catalytic cycling, , and exposure to rigorous chemical environments, − signifying that they are an attractive alternative to the widely used, but labile, thiols in noble-metal surface functionalization . The longevity of implantable electrochemical sensors, for example, is currently limited by the instability of thiol-SAMs …”

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Probing N-Heterocyclic Carbene Surfaces with Laser Desorption Ionization Mass Spectrometry

et al. 2021

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The proliferation of N-heterocyclic carbene (NHC) self-assembled monolayers (SAMs) on gold surfaces stems from their exceptional stability compared to conventional thiol-SAMs. The prospect of biological applications for NHC-SAMs on gold shows the need for biocompatible techniques (e.g., large biomolecule detection and high throughput) that assesses SAM molecular composition. Herein, we demonstrate that laser desorption ionization mass spectrometry (LDI-MS) is a powerful and facile probe of NHC surface chemistry. LDI-MS of prototypical imidazole-NHC-and benzimidazole-NHC-functionalized AuNPs yields exclusively [NHC 2 Au] + ions and not larger gold clusters. Employing benzimidazole-NHC isotopologues, we explore how monolayers pack on a single AuNP and the lability of the NHCs once ligated. Quantitative analysis of the homoleptic and heteroleptic [NHC 2 Au] + ions is performed by comparing to a binomial model representative of a randomized monolayer. Lastly, the reduction of nitro-NHC-AuNPs to amine-NHC-AuNPs is tracked via LDI-MS signals, illustrating the ability of LDI-MS to probe postsynthetic modifications of the anchored NHCs, which is critical for current and future applications of NHC surfaces.

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Controlled growth of ordered monolayers of N-heterocyclic carbenes on silicon

Cited by 48 publications

References 58 publications

Reversible Self‐Assembly of an N‐Heterocyclic Carbene on Metal Surfaces

Reversible Self‐Assembly of an N‐Heterocyclic Carbene on Metal Surfaces

A strongly twisted SiSi bond with resemblance to a buckled dimer in an unexpected isomer of hexasilabenzene

Probing N-Heterocyclic Carbene Surfaces with Laser Desorption Ionization Mass Spectrometry

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