1D and 2D Graphdiynes: Recent Advances on the Synthesis at Interfaces and Potential Nanotechnological Applications

Chen, Zhi; Molina-Jirón, Concepción; Klyatskaya, Svetlana; Klappenberger, Florian; Rüben, Mario

doi:10.1002/andp.201700056

Cited by 44 publications

(20 citation statements)

References 100 publications

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“…The main drive behind this movement originates from the outstanding mechanical and electronic properties of graphene and other 2D materials promising a plethora of new applications in a wide range of fields. Recently, in addition to the popular sp 2 carbon materials, also 1D and 2D carbon‐allotropes such as graphyne and graphdiyne have gained widespread attention because of their potential to outrival graphene regarding specific applications partly due to their inherent semiconducting electronic properties and nanoporous structures . Yet, the reliable fabrication of such structures with desired purity still remains challenging.…”

Section: Introductionmentioning

confidence: 99%

On‐Surface Activation of Trimethylsilyl‐Terminated Alkynes on Coinage Metal Surfaces

Zhang

Chen

et al. 2019

ChemPhysChem

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The controlled attachment of protecting groups combined with the ability to selectively abstract them is central to organic synthesis. The trimethylsilyl (TMS) functional group is a popular protecting group in solution. However, insights on its activation behavior under ultra-high vacuum (UHV) and surface-confined conditions are scarce. Here we investigate a series of TMSprotected alkyne precursors via scanning tunneling microscopy (STM) regarding their compatibility with organic molecular beam epitaxy (OMBE) and their potential deprotection on various coinage metal surfaces. After in-situ evaporation on the substrates held in UHV at room temperature, we find that all molecules arrived and adsorbed as intact units forming ordered supramolecular aggregates stabilized by non-covalent interac-tions. Thus, TMS-functionalized alkyne precursors with weights up to 1100 atomic mass units are stable against OMBE evaporation in UHV. Furthermore, the TMS activation through thermal annealing is investigated with STM and X-ray photoelectron spectroscopy (XPS). We observe that deprotection starts to occur between 400 K and 500 K on the copper and gold surfaces, respectively. In contrast, on silver surfaces, the TMS-alkyne bond remains stable up to temperatures where molecular desorption sets in ( � 600 K). Hence, TMS functional groups can be utilized as leaving groups on copper and gold surfaces while they serve as protecting groups on silver surfaces.

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Section: Introductionmentioning

confidence: 99%

On‐Surface Activation of Trimethylsilyl‐Terminated Alkynes on Coinage Metal Surfaces

Zhang

Chen

et al. 2019

ChemPhysChem

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“…Conjugated diynes and polyynes constitute important core structures in natural products, supramolecular compounds, materials and polymers . Numerous methods exist for the construction of the rigid diyne moiety, with metal‐catalyzed oxidative homocoupling of terminal alkynes, for example, Glaser, Eglinton and Hay coupling reactions, representing the most important method for the preparation of symmetrical 1,3‐diynes (Scheme ) .…”

Section: Introductionmentioning

confidence: 99%

Unraveling the Mechanism of 1,3‐Diyne Cross‐Metathesis Catalyzed by Silanolate‐Supported Tungsten Alkylidyne Complexes

Schnabel

Melcher

Brandhorst

et al. 2018

Chemistry A European J

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The benzylidyne complex [PhC≡W{OSi(OtBu) } ] (1) catalyzed the cross-metathesis between 1,4-bis(trimethylsilyl)-1,3-butadiyne (2) and symmetrical 1,3-diynes (3) efficiently, which gave access to TMS-capped 1,3-diynes RC≡C-C≡CSiMe (4). Diyne cross-metathesis (DYCM) studies with C-labeled diyne PhC≡ C- C≡CPh (3*) revealed that this reaction proceeds through reversible carbon-carbon triple-bond cleavage and formation according to the conventional mechanism of alkyne metathesis. The reaction between 1 and 3* afforded the 3-phenylpropynylidyne complex PhC≡ C- C≡W{OSi(OtBu) } ] (5*), indicating that alkynylalkylidyne complexes are likely to act as catalytically active species. Attempts to isolate 5* from mixtures of 1 and 3* afforded crystals of the ditungsten 2-butyne-1,4-diylidyne complex [(tBuO) SiO} W≡ C- C≡ C- C≡W{OSi(OtBu) } ] (6*), which was additionally characterized by X-ray diffraction analysis. Depolymerization-macrocyclization of a carbazole-butadiyne polymer, obtained from 3,6-diethynyl-9-dodecylcarbazole (7) under copper-catalyzed Hay coupling conditions, was also efficiently catalyzed by 1 and afforded a mixture of mono-, diyne- and triyne-containing tetrameric macrocycles, revealing that diyne disproportionation into monoynes and triynes occurs as a slow side reaction that interferes with a high diyne metathesis selectivity. Potential catalytic pathways were studied by means of quantum-chemical calculations, and kinetic studies were performed to substantiate an α,α-mechanism for the catalytic diyne metathesis reaction, which involves intermediate alkynylalkylidyne and α,α'-dialkynylmetallacyclobutadiene intermediates.

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“…24 Due to the fascinating structures and particular electronic properties, graphyne materials show promising applications in catalysts, hydrogen storage, anode materials, optoelectronic devices, biomedicine and therapy,etc . 22,23,[25][26][27][28][29] More interestingly, the graphyne molecules have recently aroused extensive attention of theoretical researchers in the field of nonlinear optics. In 2016, Chakraborti 30 theoretically investigated the NLO properties of donor-acceptor substituted graphyne structures.…”

Section: Introductionmentioning

confidence: 99%

Effects of the Atomic Number of Alkali Atom and Pore Size of Graphyne on the Second Order Nonlinear Optical Response of Superalkali Salts of Graphynes OM3+@GYs– (M = Li, Na, and K)

Hou

Feng

et al. 2020

Preprint

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Based on the combination of novel carbon material graphynes (GYs) and superalkalis (OM 3), a class of graphyne superalkali complexes, OM 3 + @(GY/GDY/GTY)-(M = Li, Na, and K), have been designed and investigated by density functional theory method. Computational results reveal that these complexes with high stability can be regarded as novel superalkali salts of graphynes due to electron transfer from OM 3 to GYs. For second order nonlinear optical response, these superalkali salts exhibit large first hyperpolarizabilities (β 0). Two important effects on β 0 values are found, namely the atomic number of alkali atom in superalkali and the pore size of graphyne. Integrating the two effects, the selected combination of OLi3 with large pore size GTY can bring the considerable β 0 value (6.5×10 5 au), which is a new record for superatom-doped graphynes. In the resulting complex, the OLi 3 molecule is located at the center of the pore of GTY, forming a planar structure with the highest stability among these salts. Besides large β 0 values, these superalkali salts of graphynes have deep-ultraviolet working region, hence can be considered as a new kind of high-performance deep-ultraviolet NLO molecules.

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1D and 2D Graphdiynes: Recent Advances on the Synthesis at Interfaces and Potential Nanotechnological Applications

Cited by 44 publications

References 100 publications

On‐Surface Activation of Trimethylsilyl‐Terminated Alkynes on Coinage Metal Surfaces

On‐Surface Activation of Trimethylsilyl‐Terminated Alkynes on Coinage Metal Surfaces

Unraveling the Mechanism of 1,3‐Diyne Cross‐Metathesis Catalyzed by Silanolate‐Supported Tungsten Alkylidyne Complexes

Effects of the Atomic Number of Alkali Atom and Pore Size of Graphyne on the Second Order Nonlinear Optical Response of Superalkali Salts of Graphynes OM3+@GYs– (M = Li, Na, and K)

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