Interfacial transmetallation synthesis of a platinadithiolene nanosheet as a potential 2D topological insulator.

The construction of two-dimensional metal complex materials is fascinating because of the structural and functional diversity of these materials. Previously, we have reported the synthesis of electroconductive nickelladithiolene (NiDT) and palladadithiolene (PdDT) nanosheets using benzenehexathiol (BHT). Down the group from Ni, Pd to Pt, there is a distinct positive shift in the reduction potential; as a result, it becomes synthetically more challenging to stabilize Pt2+ than to form metallic Pt(0) in the presence of BHT as a reducing agent. Herein, a novel synthetic strategy for the preparation of platinadithiolene nanosheet (PtDT) using a dibutyltin-protected BHT ligand is reported, leading to transmetallation in the presence of dioxygen. Both free-standing stacked sheets and atomic layer sheets were obtained and characterized by microscopic techniques such as AFM, SEM, and TEM. To study the morphology of the sheets and determine their charge neutrality, X-ray photoelectron (XP) and infrared (IR) spectroscopic techniques were used. Powder X-ray diffraction analysis of the multilayer PtDT indicates a half-way slipped hexagonal configuration in the P3[combining macron]1m space group. The band structure of this PtDT exhibits a band gap at the Fermi level, which is different from that of NiDT in the staggered configuration, and a Dirac gap, indicating the possibility of 2D topological insulation at room temperature. PtDT is insulating but chemically activated by oxidation with I2 to increase the conductivity by more than 106 folds up to 0.39 S cm-1. The MDT sheets exhibit electrocatalytic activity for the hydrogen evolution reaction, and the activity order is NiDT < PdDT < PtDT.

Coordination nanosheets (CONASHs): strategies, structures and functions.

Nanosheets, which are two-dimensional polymeric materials, remain among the most actively researched areas of chemistry and physics this decade. Generally, nanosheets are inorganic materials created from bulk crystalline layered materials and have fascinating properties and functionalities. An emerging alternative is molecule-based nanosheets containing organic molecular components. Molecule-based nanosheets offer great diversity because their molecular, ionic, and atomic constituents can be selected and combined to produce a wide variety of nanosheets. The present article focuses on coordination nanosheets (CONASHs), a class of molecule-based nanosheets comprising organic ligand molecules and metal ions/atoms in a framework linked with coordination bonds. Following the Introduction, Section 2 describes CONASHs, including their definition, design, synthetic procedures, and characterisation techniques. Section 3 introduces various examples of CONASHs, and Section 4 explores their functionality and possible applications. Section 5 describes an outlook for the research field of CONASHs.

Liquid/Liquid Interfacial Synthesis of a Click Nanosheet.

A liquid/liquid interfacial synthesis is employed, for the first time, to synthesize a covalent two-dimensional polymer nanosheet. Copper-catalyzed azide-alkyne cycloaddition (CuAAC) between a three-way terminal alkyne and azide at a water/dichloromethane interface generates a 1,2,3-triazole-linked nanosheet. The resultant nanosheet, with a flat and smooth texture, has a maximum domain size of 20 µm and minimum thickness of 5.3 nm. The starting monomers in the organic phase and the copper catalyst in the aqueous phase can only meet at the liquid/liquid interface as a two-dimensional reaction space; this allows them to form the two-dimensional polymer. The robust triazole linkage generated by irreversible covalent-bond formation allows the nanosheet to resist hydrolysis under both acidic and alkaline conditions, and to endure pyrolysis up to more than 300 °C. The coordination ability of the triazolyl group enables the nanosheet to act as a reservoir for metal ions, with an affinity order of Pd2+ >Au3+ >Cu2+ .

Interfacial Synthesis of Electrically Conducting Palladium Bis(dithiolene) Complex Nanosheet.

The synthesis of palladium bis(dithiolene) complex nanosheets (PdDt) possessing a kagome-type lattice structure was performed via interfacial reaction between metal salt in aqueous phase and dithiolato ligand in organic phase. The PdDt nanosheets were characterised by AFM, STM, TEM revealing flat and sheet-like morphology; IR, UV spectroscopy show the corresponding coordination connectivity between metal and ligand, followed by powder X-ray diffraction and SAED, which determined nanosheets to be structurally similar to previously reported nickel bis(dithiolene) complex nanosheets NiDt.

Redox control and high conductivity of nickel bis(dithiolene) complex π-nanosheet: a potential organic two-dimensional topological insulator.

A bulk material comprising stacked nanosheets of nickel bis(dithiolene) complexes is investigated. The average oxidation number is -3/4 for each complex unit in the as-prepared sample; oxidation or reduction respectively can change this to 0 or -1. Refined electrical conductivity measurement, involving a single microflake sample being subjected to the van der Pauw method under scanning electron microscopy control, reveals a conductivity of 1.6 × 10(2) S cm(-1), which is remarkably high for a coordination polymeric material. Conductivity is also noted to modulate with the change of oxidation state. Theoretical calculation and photoelectron emission spectroscopy reveal the stacked nanosheets to have a metallic nature. This work provides a foothold for the development of the first organic-based two-dimensional topological insulator, which will require the precise control of the oxidation state in the single-layer nickel bisdithiolene complex nanosheet (cf. Liu, F. et al. Nano Lett. 2013, 13, 2842).