Browse
Submit Data
Databases
API
Help

Dataset Information

19 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Cooperation of N-Heterocyclic Carbenes on a Gold Surface.

ABSTRACT: Atomically precise tailoring of interface structures is crucial for developing functional materials. We demonstrate an N-heterocyclic carbene (NHC) based molecular tool, which modifies the structure of a gold surface with atomic accuracy by the formation of gold nanorods. After adsorption on the gold surface, individual surface atoms are pulled out by the NHCs, generating single-atom surface defects and mobile NHC-Au species. Atomistic calculations reveal that these molecular "ballbots" can act as assembling tools to dislocate individual surface atoms. The predicted functionality of these carbene-based complexes is confirmed by scanning tunneling microscopy measurements. Cooperative operation of these NHC-Au species induces a step-wise formation of gold nanorods. Consequently, the surface is re-structured by a zipper-type mechanism. Our work presents a foundation to utilize molecular-based nanotools to design surface structures.

SUBMITTER: Amirjalayer S

PROVIDER: S-EPMC7702088 | biostudies-literature | 2020 Nov

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Cooperation of N-Heterocyclic Carbenes on a Gold Surface.

Amirjalayer Saeed S Bakker Anne A Freitag Matthias M Glorius Frank F Fuchs Harald H

Angewandte Chemie (International ed. in English) 20201004 47

Atomically precise tailoring of interface structures is crucial for developing functional materials. We demonstrate an N-heterocyclic carbene (NHC) based molecular tool, which modifies the structure of a gold surface with atomic accuracy by the formation of gold nanorods. After adsorption on the gold surface, individual surface atoms are pulled out by the NHCs, generating single-atom surface defects and mobile NHC-Au species. Atomistic calculations reveal that these molecular "ballbots" can act ...[more]

PMID: 32822093

Similar Datasets

Zwitterionic dithiocarboxylates derived from N-heterocyclic carbenes: coordination to gold surfaces.

Project description:The zwitterionic dithiocarboxylates 1(+)-CS(2)(-)-4(+)-CS(2)(-) were prepared by reacting the corresponding N-heterocyclic carbenes 1,3-bis(2,6-diisoproylphenyl)imidazol-2-ylidene (1), 1,3-diisopropylimidazol-2-ylidene (2), 1,3-dibenzylimidazol-2-ylidene (3) and 1,3-diethylbenzimidazol-2-ylidene (4) with CS(2). In the latter two cases, the corresponding N-heterocylic carbene was generated in situ. Compounds 2(+)-CS(2)(-)-4(+)-CS(2)(-) were structurally characterised by single-crystal X-ray diffraction studies. The chemisorption of these zwitterionic dithiocarboxylates on solid gold substrates was investigated in situ and in real time by optical second harmonic generation (SHG). The resulting thin films were exemplarily characterised by near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and X-ray photoelectron spectroscopy (XPS) in the case of 1(+)-CS(2)(-) and 2(+)-CS(2)(-), revealing the formation of almost contamination-free self-assembled monolayers, which exhibit a remarkable degree of orientational order.

| S-EPMC3737455 | biostudies-literature

N-Heterocyclic Carbenes: Molecular Porters of Surface Mounted Ru-Porphyrins.

Project description:Ru-porphyrins act as convenient pedestals for the assembly of N-heterocyclic carbenes (NHCs) on solid surfaces. Upon deposition of a simple NHC ligand on a close packed Ru-porphyrin monolayer, an extraordinary phenomenon can be observed: Ru-porphyrin molecules are transferred from the silver surface to the next molecular layer. We have investigated the structural features and dynamics of this portering process and analysed the associated binding strengths and work function changes. A rearrangement of the molecular layer is induced by the NHC uptake: the NHC selective binding to the Ru causes the ejection of whole porphyrin molecules from the molecular layer on silver to the layer on top. This reorganisation can be reversed by thermally induced desorption of the NHC ligand. We anticipate that the understanding of such mass transport processes will have crucial implications for the functionalisation of surfaces with carbenes.

| S-EPMC10092334 | biostudies-literature

Covalent Adsorption of N-Heterocyclic Carbenes on a Copper Oxide Surface.

Project description:Tuning the properties of oxide surfaces through the adsorption of designed ligands is highly desirable for several applications, such as catalysis. N-Heterocyclic carbenes (NHCs) have been successfully employed as ligands for the modification of metallic surfaces. On the other hand, their potential as modifiers of ubiquitous oxide surfaces still needs to be developed. Here we show that a model NHC binds covalently to a copper oxide surface under UHV conditions. In particular, we report the first example of a covalent bond between NHCs and oxygen atoms from the oxide layer. This study demonstrates that NHC can also act as a strong anchor on oxide surfaces.

| S-EPMC9479068 | biostudies-literature

Halogen Complexes of Anionic N-Heterocyclic Carbenes.

Project description:The lithium complexes [(WCA-NHC)Li(toluene)] of anionic N-heterocyclic carbenes with a weakly coordinating anionic borate moiety (WCA-NHC) reacted with iodine, bromine, or CCl4 to afford the zwitterionic 2-halogenoimidazolium borates (WCA-NHC)X (X=I, Br, Cl; WCA=B(C6 F5 )3 , B{3,5-C6 H3 (CF3 )2 }3 ; NHC=IDipp=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene, or NHC=IMes=1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene). The iodine derivative (WCA-IDipp)I (WCA=B(C6 F5 )3 ) formed several complexes of the type (WCA-IDipp)I⋅L (L=C6 H5 Cl, C6 H5 Me, CH3 CN, THF, ONMe3 ), revealing its ability to act as an efficient halogen bond donor, which was also exploited for the preparation of hypervalent bis(carbene)iodine(I) complexes of the type [(WCA-IDipp)I(NHC)] and [PPh4 ][(WCA-IDipp)I(WCA-NHC)] (NHC=IDipp, IMes). The corresponding bromine complex [PPh4 ][(WCA-IDipp)2 Br] was isolated as a rare example of a hypervalent (10-Br-2) system. DFT calculations reveal that London dispersion contributes significantly to the stability of the bis(carbene)halogen(I) complexes, and the bonding was further analyzed by quantum theory of atoms in molecules (QTAIM) analysis.

| S-EPMC7986712 | biostudies-literature

N-Heterocyclic Carbene Organocatalysis: With or Without Carbenes?

Project description:In this work the mechanism of the aldehyde umpolung reactions, catalyzed by azolium cations in the presence of bases, was studied through computational methods. Next to the mechanism established by Breslow in the 1950s that takes effect through the formation of a free carbene, we have suggested that these processes can follow a concerted asynchronous path, in which the azolium cation directly reacts with the substrate, avoiding the formation of the carbene intermediate. We hereby show that substituting the azolium cation, and varying the base or the substrate do not affect the preference for the concerted reaction mechanism. The concerted path was found to exhibit low barriers also for the reactions of thiamine with model substrates, showing that this path might have biological relevance. The dominance of the concerted mechanism can be explained through the specific structure of the key transition state, avoiding the liberation of the highly reactive, and thus unstable carbene lone pair, whereas activating the substrate through hydrogen-bonding interactions. Polar and hydrogen-bonding solvents, as well as the presence of the counterions of the azolium salts facilitate the reaction through carbenes, bringing the barriers of the two reaction mechanisms closer, in many cases making the concerted path less favorable. Thus, our data show that by choosing the exact components in a reaction, the mechanism can be switched to occur with or without carbenes.

| S-EPMC7496998 | biostudies-literature

IPr# - highly hindered, broadly applicable N-heterocyclic carbenes.

Project description:IPr (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) represents the most important NHC (NHC = N-heterocyclic carbene) ligand throughout the field of homogeneous catalysis. Herein, we report the synthesis, catalytic activity, and full structural and electronic characterization of novel, sterically-bulky, easily-accessible NHC ligands based on the hash peralkylation concept, including IPr#, Np# and BIAN-IPr#. The new ligands have been commercialized in collaboration with Millipore Sigma: IPr#HCl, 915653; Np#HCl; 915912; BIAN-IPr#HCl, 916420, enabling broad access of the academic and industrial researchers to new ligands for reaction optimization and screening. In particular, the synthesis of IPr# hinges upon cost-effective, modular alkylation of aniline, an industrial chemical that is available in bulk. The generality of this approach in ligand design is demonstrated through facile synthesis of BIAN-IPr# and Np#, two ligands that differ in steric properties and N-wingtip arrangement. The broad activity in various cross-coupling reactions in an array of N-C, O-C, C-Cl, C-Br, C-S and C-H bond cross-couplings is demonstrated. The evaluation of steric, electron-donating and π-accepting properties as well as coordination chemistry to Au(i), Rh(i) and Pd(ii) is presented. Given the tremendous importance of NHC ligands in homogenous catalysis, we expect that this new class of NHCs will find rapid and widespread application.

| S-EPMC8356752 | biostudies-literature

Poly(3-hexylthiophene)s Functionalized with N-Heterocyclic Carbenes as Robust and Conductive Ligands for the Stabilization of Gold Nanoparticles.

Project description:Recently, N-heterocyclic carbenes (NHCs) are explored as anchor groups to bind organic ligands to colloidal gold (i.e. gold nanoparticles, Au NPs), yet these efforts are confined to non-conjugated ligands so far-that is, focused solely on exploiting the stability aspect. Using NHCs to link Au NPs and electronically active organic components, for example, conjugated polymers (CPs), will allow capitalizing on both the stability as well as the inherent conductivity of the NHC anchors. Here, we report three types of Br-NHC-Au-X (X=Cl, Br) complexes, which, when used as starting points for Kumada polymerizations, yield regioregular poly(3-hexylthiophenes)-NHC-Au (P3HTs-NHC-Au) with narrow molecular weight distributions. The corresponding NPs are obtained via direct reduction and show excellent thermal as well as redox stability. The NHC anchors enable electron delocalization over the gold/CP interface, resulting in an improved electrochromic response behavior in comparison with P3HT-NHC-Au.

| S-EPMC7898828 | biostudies-literature

An enantioselective Claisen rearrangement catalyzed by N-heterocyclic carbenes.

Project description:In the presence of a chiral azolium salt (10 mol %), enols and ynals undergo a highly enantioselective annulation reaction to form enantiomerically enriched dihydropyranones via an N-heterocyclic carbene catalyzed variant of the Claisen rearrangement. Unlike other azolium-catalyzed reactions, this process requires no added base to generate the putative NHC-catalyst, and our investigations demonstrate that the counterion of the azolium salt plays a key role in the formation of the catalytically active species. Detailed kinetic studies eliminate a potential 1,4-addition as the mechanistic pathway; the observed rate law and activation parameters are consistent with a Claisen rearrangement as the rate-limiting step. This catalytic system was applied to the synthesis of enantioenriched kojic acid derivatives, a reaction of demonstrated synthetic utility for which other methods for catalytic enantioselective Claisen rearrangements have not provided a satisfactory solution.

| S-EPMC2902991 | biostudies-literature

Self-assembly of N-heterocyclic carbenes on Au(111).

Project description:Although the self-assembly of organic ligands on gold has been dominated by sulfur-based ligands for decades, a new ligand class, N-heterocyclic carbenes (NHCs), has appeared as an interesting alternative. However, fundamental questions surrounding self-assembly of this new ligand remain unanswered. Herein, we describe the effect of NHC structure, surface coverage, and substrate temperature on mobility, thermal stability, NHC surface geometry, and self-assembly. Analysis of NHC adsorption and self-assembly by scanning tunneling microscopy and density functional theory have revealed the importance of NHC-surface interactions and attractive NHC-NHC interactions on NHC monolayer structures. A remarkable way these interactions manifest is the need for a threshold NHC surface coverage to produce upright, adatom-mediated adsorption motifs with low surface diffusion. NHC wingtip structure is also critical, with primary substituents leading to the formation of flat-lying NHC2Au complexes, which have high mobility when isolated, but self-assemble into stable ordered lattices at higher surface concentrations. These and other studies of NHC surface chemistry will be crucial for the success of these next-generation monolayers.

| S-EPMC8241988 | biostudies-literature

Direct amination of homoenolates catalyzed by N-heterocyclic carbenes.

Project description:N-Heterocyclic carbenes derived from N-mesityl-N-methyltriazolium salts are effective catalysts for generating homoenolate species from alpha,beta-unsaturated aldehydes. The unique intermediate adds to the electrophilic nitrogen of 1-acyl-2-aryldiazenes, and the resulting activated carbonyl unit undergoes an intramolecular acylation event. This formal [3+2] cycloaddition between alpha,beta-unsaturated aldehydes and acylaryldiazenes, catalyzed by an N-heterocyclic carbene, produces substituted pyrazolidinones in good yields. This new NHC-catalyzed reaction accommodates aromatic and alkyl alpha,beta-unsaturated aldehydes and various aromatic diazenes. A chiral triazolium salt catalyzes the formation of the pyrazolidinone product in moderate yield and good enantioselectivity. The pyrazolidinones can undergo reductive N-N bond cleavage to give beta-amino acid derivatives.

| S-EPMC2981089 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data