Fine-tuning of two-dimensional metal–organic nanostructures via alkali–pyridyl coordination

Abstract

Fine-tuning of 2D metal–organic nanostructures is realized by alkali–pyridyl coordination.

Exploiting Cooperative Catalysis for the On‐Surface Synthesis of Linear Heteroaromatic Polymers via Selective C–H Activation

“…Spontaneous dissociation of NaCl and subsequent coordination of Na adatoms with organic molecules have been reported to occur upon surface annealing at elevated temperatures. [ 28 , 29 , 30 , 31 , 32 ] However, apart from simple intramolecular reactions such as tautomeric isomerization of guanine [33] and deprotonation of terephthalic acid, [34] no Na‐assisted intermolecular coupling has been identified so far.…”

Einsatz der kooperativen Katalyse für die Oberflächensynthese linearer heteroaromatischer Polymere durch selektive C‐H‐Aktivierung

“…Spontane Dissoziation von NaCl und anschließende Koordination von Na-Adatomen mit organischen Molekülen wurde bereits beim Erwärmen von Oberflächen bei erhöhten Temperaturen beobachtet. [28][29][30][31][32] Doch abgesehen von einfachen intramolekularen Reaktionen wie der tautomeren Isomerisierung von Guanin [33] und der Deprotonierung von Terephthalsäure, [34] wurde bislang keine Na-unterstützte intermolekulare Kopplung festgestellt.…”

Construction and Structural Transformation of Metal–Organic Nanostructures Induced by Alkali Metals and Alkali Metal Salts

“…A dark protrusion could be visible at the center in a special tip state (as depicted by blue circles in Figure 1e) and was attributed to Na according to our previous reports, 18,25 which is also in good agreement with the situation on Ag(111). 22 Furthermore, additional NaCl was deposited to verify the influence of NaCl dosage on the structural diversity, which, interestingly, led to the coexistence of NaCl islands and phase I (Figure 1c), while no structural transformation was observed. DFT calculations were further carried out on the structure of phase I, and the energetically most favorable one is shown in Figure 1f.…”

“…Notably, in the previous studies, NaCl is generally known as an insulating support for decoupling 27,28 and has been recently introduced to interact with various molecular systems in the following situations. (i) Only Na cations are directly involved in the metal−organic nanostructures, forming electrostatic ionic interactions, [15][16][17][18][19][20][21][22]29 similar to the cases of pure alkali metals. (ii) Na interacts with organic molecules to construct the metal−organic motifs, while halogens further stabilize the structures, leading to structural diversity.…”

“…Metal–organic nanostructures, consisting of metal nodes and organic ligands, make up a class of structurally diverse and functionally tunable materials , and have proven to be versatile platforms in a wide range of scientific fields, including biomedicine, energy harvesting, and catalysis. , In an effort to achieve tailored properties and the desired performance, different types of metals have been integrated to regulate fundamental chemical interactions within building blocks, which range from transition metals to alkali and alkaline earth metals. − It has also aroused considerable interest in the surface science community; meanwhile, surface science techniques allow direct visualization of metal–organic nanostructures supported by solid surfaces in real space and determination of the intermolecular interactions involved. Tremendous effort has been devoted to the engineering of low-dimensional metal–organic architectures on surfaces mainly based on directional coordination bonds with d-block transition metals embedded, − as well as flexible coordination provided by f-block lanthanides. − Recently, alkali metals derived from either pure alkali metals − or alkali halides (e.g., NaCl and KBr) − have been introduced to interact with organic molecules on surfaces via isotropic electrostatic ionic bonding, enabling the structural diversity of metal–organic nanostructures. , In these cases, both pure alkali metals and alkali metal salts are applied to provide metal centers. However, their differences in the construction of alkali-based metal–organic nanostructures as alkali metal providers have been less discussed, and the corresponding influence on the structural diversity remains elusive.…”