Stabilizing and Organizing Bi3Cu4 and Bi7Cu12 Nanoclusters in Two‐Dimensional Metal–Organic Networks

Yan, Linghao; Xia, Bowen; Zhang, Qiushi; Kuang, Guowen; Xu, Hu; Li, Jun; Liu, Pei Nian; Lin, Nian

doi:10.1002/anie.201800906

Cited by 14 publications

(8 citation statements)

References 57 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…5a bottom). The similar situation that only the metal atoms with a bigger size in the heterometallic clusters are discernable by STM was also reported by Yan et al recently 30 .…”

Section: Structures Of the Coordinated Multi-ce-containing Clusterssupporting

confidence: 86%

“…3b. The similar phenomenon was also found by Yan et al 30 showing that the evaporated metal atoms were bridged by the intrinsic adatoms to form coordinated heterometallic clusters on surfaces. The Ce-Ce distance in the optimized model of the Ce 2 Au 2 (CN) 6 motif (4.95 Å) is consistent with the experimental value (4.7 ± 0.4 Å) by taking the measurement error into account.…”

Section: Structures Of the Coordinated Multi-ce-containing Clusterssupporting

confidence: 83%

“…Recently, a series of Ln-organic hybrids have been constructed via on-surface coordination, in which either single Ln atoms [14][15][16][17][18][19][20][21][22][23][24] or molecule-bridged Ln dimers 17 were identified as the coordination centers. Meanwhile, the achievement of non-lanthanide metallic clusters stabilized by organic ligands on surfaces were also reported [25][26][27][28][29][30] . Nevertheless, the onsurface preparation of coordination complexes formed by TMbridged multi-Ln-containing heterometallic clusters has yet to be realized.…”

mentioning

confidence: 90%

See 2 more Smart Citations

On-surface preparation of coordinated lanthanide-transition-metal clusters

Liu

et al. 2021

Nat Commun

View full text Add to dashboard Cite

The study of lanthanide (Ln)-transition-metal (TM) heterometallic clusters which play key roles in various high-tech applications is a rapid growing field of research. Despite the achievement of numerous Ln-TM cluster compounds comprising one Ln atom, the synthesis of Ln-TM clusters containing multiple Ln atoms remains challenging. Here, we present the preparation and self-assembly of a series of Au-bridged heterometallic clusters containing multiple cerium (Ce) atoms via on-surface coordination. By employing different pyridine and nitrile ligands, the ordered coordination assemblies of clusters containing 2, 3 and 4 Ce atoms bridged by Au adatoms are achieved on Au(111) and Au(100), as revealed by scanning tunneling microscopy. Density functional theory calculations uncover the indispensable role of the bridging Au adatoms in constructing the multi-Ce-containing clusters by connecting the Ce atoms via unsupported Ce-Au bonds. These findings demonstrate on-surface coordination as an efficient strategy for preparation and organization of the multi-Ln-containing heterometallic clusters.

show abstract

“…5a bottom). The similar situation that only the metal atoms with a bigger size in the heterometallic clusters are discernable by STM was also reported by Yan et al recently 30 .…”

Section: Structures Of the Coordinated Multi-ce-containing Clusterssupporting

confidence: 86%

Section: Structures Of the Coordinated Multi-ce-containing Clusterssupporting

confidence: 83%

mentioning

confidence: 90%

See 1 more Smart Citation

On-surface preparation of coordinated lanthanide-transition-metal clusters

Liu

et al. 2021

Nat Commun

View full text Add to dashboard Cite

show abstract

“…In fact, there are several recent predictions based on ab initio modelling suggesting that honeycomb and kagome metal‐organic networks could host exotic quantum phases, for example, topological insulators . However, most of the metal‐organic networks that have been obtained are using 3d transition metals, with only a few reports on heavy metals which can provide strong spin‐orbit coupling …”

Section: Figurementioning

confidence: 99%

On‐Surface Assembly of Au‐Dicyanoanthracene Coordination Structures on Au(111)

et al. 2019

Self Cite

View full text Add to dashboard Cite

On-surface metal-organic coordination provides a promising way for synthesizing different two-dimensional lattice structures that have been predicted to possess exotic electronic properties. Using scanning tunneling microscopy (STM) and spectroscopy (STS), we studied the supramolecular self-assembly of 9,10-dicyanoanthracene (DCA) molecules on the Au(111) surface. Close-packed islands of DCA molecules and Au-DCA metal-organic coordination structures coexist on the Au(111) surface. Ordered DCA 3 Au 2 metal-organic networks have a structure combining a honeycomb lattice of Au atoms with a kagome lattice of DCA molecules. Low-temperature STS experiments demonstrate the presence of a delocalized electronic state containing contributions from both the gold atom states and the lowest unoccupied molecular orbital of the DCA molecules. These findings are important for the future search of topological phases in metal-organic networks combining honeycomb and kagome lattices with strong spin-orbit coupling in heavy metal atoms.It is well-known that the exciting electronic properties of graphene are intimately linked to its honeycomb lattice with a two-atom unit cell. [1] This results in the formation of Dirac cones in the band structure and the linear dispersion around the K points (at the corners of the Brillouin zone). This is a generic property of any honeycomb lattice and has sparked interest in "artificial graphene": engineered systems that have the same structure. [2][3][4][5][6] There are other lattice geometries that have the potential to host exotic electronic phases. For example, the kagome lattice has the same Dirac band structure as the honeycomb lattice, but with an additional flat band [7] pinned to the top (or bottom) of the Dirac band. Furthermore, these systems can be driven into topological phases by adding spinorbit coupling. This opens gaps at the band crossings (the Dirac points) which host topological states in finite structures. [8][9][10] Metal-organic structures have been synthesized on surfaces following the concepts of supramolecular coordination chemistry. [11,12] Their architectures depend on the chemistry of the metal centres with organic linkers and on their interactions with the surface. [13] Over the past two decades, metal-organic networks with various lattice structures have been fabricated using different combinations of metal atoms and organic molecules. In addition to fabricating e. g. simple square geometry, metal-organic networks with honeycomb and kagome lattices have been formed. [14] These hold promise for hosting exotic band structures, especially when combined with heavy metal atoms. In fact, there are several recent predictions based on ab initio modelling suggesting that honeycomb and kagome metal-organic networks could host exotic quantum phases, for example, topological insulators. [15][16][17][18][19] However, most of the metal-organic networks that have been obtained are using 3d transition metals, with only a few reports on heavy metals which can provide strong spin-orbit ...

show abstract

“…Thus, on-surface Ullmann-like coupling reaction based on non-metallic surfaces requires further dedicated explorations for the fabrication of tailored nanoarchitectures, and the substrate catalytic activity also needs to be properly considered. Bismuth, known as a typical semimetal with the reduced surface activity, was introduced recently in the form of Bi-metal complex into both the molecular self-assembly and on-surface reaction [31][32][33] , whereas the catalytic performance of bismuth was still under debate, to some extent. For instance, it was demonstrated that the DBBA precursor got completely desorbed on the bismuth decorated Au(111) surface and therefore no Ullmann-like coupling was observed 31 .…”

mentioning

confidence: 99%

Initiating Ullmann-like coupling of Br2Py by a semimetal surface

Wang

et al. 2021

Sci Rep

View full text Add to dashboard Cite

Intensive efforts have been devoted to surface Ullmann-like coupling in recent years, due to its appealing success towards on-surface synthesis of tailor-made nanostructures. While attentions were mostly drawn on metallic substrates, however, Ullmann dehalogenation and coupling reaction on semimetal surfaces has been seldom addressed. Herein, we demonstrate the self-assembly of 2, 7-dibromopyrene (Br2Py) and the well controllable dehalogenation reaction of Br2Py on the Bi(111)–Ag substrate with a combination of scanning tunnelling microscopy (STM) and density functional theory calculations (DFT). By elaborately investigating the reaction path and formed organic nanostructures, it is revealed that the pristinely inert bismuth layer supported on the silver substrate can initiate Ullmann-like coupling in a desired manner by getting alloyed with Ag atoms underneath, while side products have not been discovered. By clarifying the pristine nature of Bi–Ag(111) and Ullmann-like reaction mechanisms, our report proposes an ideal template for thoroughly exploring dehalogenative coupling reaction mechanisms with atomic insights and on-surface synthesis of carbon-based architectures.

show abstract

Stabilizing and Organizing Bi₃Cu₄ and Bi₇Cu₁₂ Nanoclusters in Two‐Dimensional Metal–Organic Networks

Cited by 14 publications

References 57 publications

On-surface preparation of coordinated lanthanide-transition-metal clusters

On-surface preparation of coordinated lanthanide-transition-metal clusters

On‐Surface Assembly of Au‐Dicyanoanthracene Coordination Structures on Au(111)

Initiating Ullmann-like coupling of Br2Py by a semimetal surface

Contact Info

Product

Resources

About