N‐Heterocyclic Carbenes Reduce and Functionalize Copper Oxide Surfaces in One Pot

Veinot, Alex J.; al-rashed, abrar; Padmos, J. Daniel; Singh, Ishwar; Lee, Dianne S; Narouz, Mina R.; Lummis, Paul A.; Baddeley, Christopher J.; Crudden, Cathleen M.; Horton, J. Hugh

doi:10.1002/chem.202002308

Cited by 23 publications

(32 citation statements)

References 31 publications

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“…Since it was discovered that N-heterocyclic carbenes (NHCs) are stable carbenes that can be crystallized, their unique properties have been eagerly explored in novel organometallic materials, metallopharmaceuticals, catalysts, and surface functionalization . Because NHCs are able to coordinate to transition metals as well as p-block elements, they have been excellent ligands to diverse surfaces ranging from metals to semiconductors and, more recently, oxides. − Examples illustrating functional materials with NHC-stabilized interfaces include Ru nanoparticles for hydrogenation catalysis and soluble Au nanorods for phototherapy. , One of the key properties of these ligands is that their substituents are amenable by synthesis. Therefore, on extended metal surfaces they can offer anchors for tethering further functional groups, such as catalytically active complexes, or provide chiral centers exploited in unidirectional molecular rotation and chiral sensing …”

Section: Introductionmentioning

confidence: 99%

Assembly and Manipulation of a Prototypical N-Heterocyclic Carbene with a Metalloporphyrin Pedestal on a Solid Surface

et al. 2021

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The controlled arrangement of N-heterocyclic carbenes (NHCs) on solid surfaces is a current challenge of surface functionalization. We introduce a strategy of using Ru porphyrins in order to control both the orientation and lateral arrangement of NHCs on a planar surface. The coupling of the NHC to the Ru porphyrin is a facile process which takes place on the interface: we apply NHCs as functional, robust pillars on welldefined, preassembled Ru porphyrin monolayers on silver and characterize these interfaces with atomic precision via a battery of experimental techniques and theoretical considerations. The NHCs assemble at room temperature modularly and reversibly on the Ru porphyrin arrays. We demonstrate a selective and complete functionalization of the Ru centers. With its binding, the NHC modifies the interaction of the Ru porphyrin with the Ag surface, displacing the Ru atom by 1 Å away from the surface. This arrangement of NHCs allows us to address individual ligands by controlled manipulation with the tip of a scanning tunneling microscope, creating patterned structures on the nanometer scale.

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Section: Introductionmentioning

confidence: 99%

Assembly and Manipulation of a Prototypical N-Heterocyclic Carbene with a Metalloporphyrin Pedestal on a Solid Surface

et al. 2021

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“…In this work, we aim at systematically investigating the chemical nature of the methylated NHC ligand (1,3-dimethylbenzimidazolylidene, simplified as NHC Me , Figure a) on various well-defined transition metal surfaces by density functional theory (DFT) calculations. Note that the studied NHC Me ligand has been applied in experiment to form high-quality and densely packed SAMs on Au, Ag, and Cu surfaces. ,,, We considered the four metals from the experimental list (Au, Ag, Cu, and Pt ,− ) and added the unexperimented Ru ,,− and one early transition metal Ti for our theoretical investigation. For comparison, we also examined the hydrogen-terminated nonmetal Si (111) surface, which can undergo carbene functionalization forming persistent C–Si linkages .…”

Section: Introductionmentioning

confidence: 99%

Theoretical Investigation on the Adsorption and Interface Bonding between N-Heterocyclic Carbenes and Metal Surfaces

2021

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Compared with the well-established metal−thiolate interfaces, the study of the interface between N-heterocyclic carbenes (NHCs) and the metal substrate is much less explored, and the majority of work has been limited to the surfaces of Au, Ag, and Cu. The interface is closely related to the combination modes of NHCs on solid surfaces, which determines the morphologies of NHC-based self-assembly monolayers (SAMs). In this work, we performed theoretical investigations to take a fundamental look at how the methylated carbene (NHC Me ) ligands bind to the different solid surfaces (Au111, Ag111, Cu111, Ti0001, Pt111, Ru0001, and H-terminated Si111). On the clean surfaces without adatoms, the NHC Me vertically binds with surface atoms by a single C−M bond. Compared with the experimentally characterized NHC−Au(111) interface, the stronger adsorption of NHC Me on Pt (111) and Ti (0001) and the comparable binding strength on Ru (0001) indicate that they hold great promise to form highly strong and stable SAMs. Moreover, on the adatom surfaces, a dimer complex, NHC Me −M ad −NHC Me , can be formed and is energetically more favored than the upright adsorption. Interestingly, the distance of adatoms from the surface, which is an intrinsic property of the transition metals, plays an important role in determining the molecular orientations of NHC Me . The longer distance of coinage adatoms results in a nearly flatlying "T-shaped" binding mode. By contrast, the shorter distance of adatoms on Pt (111) and Ru (0001) brings a winglike "Vshaped" configuration, which has thus far not been revealed in experiment. The results will invite the experimental design of stable NHC-based SAMs with attractive interface features beyond the coinage metals.

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“…Another peak was detected at 916.5 and was correlated to Cu 1 + species. [16] The nanolayer-coated copper film was exposed to oxidizing conditions (100 °C, air, 4 h) to assess the functionality of the organic layer for corrosion inhibition. The XPS spectrum of nanolayer-coated copper film did not noticeably change after exposure to oxidizing conditions (Figure 3a, spectrum ii).…”

Section: Resultsmentioning

confidence: 99%

“…The strong and stable anchoring of NHCs to coinage metals has led to their wide utilization for monolayer formation [14] . It has been demonstrated that NHCs can bind to copper surfaces [15] and that NHCs’ deposition led to copper‐oxide reduction [16] . However, the limited stability of NHC monolayers under harsh conditions and challenges in their uniform deposition have restricted their applicability for mitigating copper films oxidation.…”

Section: Introductionmentioning

confidence: 99%

N‐Heterocyclic Carbene Based Nanolayer for Copper Film Oxidation Mitigation

et al. 2022

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The wide use of copper is limited by its rapid oxidation. Main oxidation mitigation approaches involve alloying or surface passivation technologies. However, surface alloying often modifies the physical properties of copper, while surface passivation is characterized by limited thermal and chemical stability. Herein, we demonstrate an electrochemical approach for surface‐anchoring of an N‐heterocyclic carbene (NHC) nanolayer on a copper electrode by electro‐deposition of alkyne‐functionalized imidazolium cations. Water reduction reaction generated a high concentration of hydroxide ions that induced deprotonation of imidazolium cations and self‐assembly of NHCs on the copper electrode. In addition, alkyne group deprotonation enabled on‐surface polymerization by coupling surface‐anchored and solvated NHCs, which resulted in a 2 nm thick NHC‐nanolayer. Copper film coated with a NHC‐nanolayer demonstrated high oxidation resistance at elevated temperatures and under alkaline conditions.

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N‐Heterocyclic Carbenes Reduce and Functionalize Copper Oxide Surfaces in One Pot

Cited by 23 publications

References 31 publications

Assembly and Manipulation of a Prototypical N-Heterocyclic Carbene with a Metalloporphyrin Pedestal on a Solid Surface

Assembly and Manipulation of a Prototypical N-Heterocyclic Carbene with a Metalloporphyrin Pedestal on a Solid Surface

Theoretical Investigation on the Adsorption and Interface Bonding between N-Heterocyclic Carbenes and Metal Surfaces

N‐Heterocyclic Carbene Based Nanolayer for Copper Film Oxidation Mitigation

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