Crystalline Graphdiyne Nanosheets Produced at a Gas/Liquid or Liquid/Liquid Interface

Synthetic two-dimensional polymers, or bottom-up nanosheets, are ultrathin polymeric frameworks with in-plane periodicity. They can be synthesized in a direct, bottom-up fashion using atomic, ionic, or molecular components. However, few are based on carbon–carbon bond formation, which means that there is a potential new field of investigation into these fundamentally important chemical bonds. Here, we describe the bottom-up synthesis of all-carbon, π-conjugated graphdiyne nanosheets. A liquid/liquid interfacial protocol involves layering a dichloromethane solution of hexaethynylbenzene on an aqueous layer containing a copper catalyst at room temperature. A multilayer graphdiyne (thickness, 24 nm; domain size, >25 μm) emerges through a successive alkyne–alkyne homocoupling reaction at the interface. A gas/liquid interfacial synthesis is more successful. Sprinkling a very small amount of hexaethynylbenzene in a mixture of dichloromethane and toluene onto the surface of the aqueous phase at room temperature generated single-crystalline graphdiyne nanosheets, which feature regular hexagonal domains, a lower degree of oxygenation, and uniform thickness (3.0 nm) and lateral size (1.5 μm)

Crystalline Graphdiyne Nanosheets Produced at a Gas/Liquid or Liquid/Liquid Interface

Synthetic two-dimensional polymers, or bottom-up nanosheets, are ultrathin polymeric frameworks with in-plane periodicity. They can be synthesized in a direct, bottom-up fashion using atomic, ionic, or molecular components. However, few are based on carbon–carbon bond formation, which means that there is a potential new field of investigation into these fundamentally important chemical bonds. Here, we describe the bottom-up synthesis of all-carbon, π-conjugated graphdiyne nanosheets. A liquid/liquid interfacial protocol involves layering a dichloromethane solution of hexaethynylbenzene on an aqueous layer containing a copper catalyst at room temperature. A multilayer graphdiyne (thickness, 24 nm; domain size, >25 μm) emerges through a successive alkyne–alkyne homocoupling reaction at the interface. A gas/liquid interfacial synthesis is more successful. Sprinkling a very small amount of hexaethynylbenzene in a mixture of dichloromethane and toluene onto the surface of the aqueous phase at room temperature generated single-crystalline graphdiyne nanosheets, which feature regular hexagonal domains, a lower degree of oxygenation, and uniform thickness (3.0 nm) and lateral size (1.5 μm)

π‑Conjugated Trinuclear Group‑9 Metalladithiolenes with a Triphenylene Backbone

Previously, we synthesized π-conjugated trinuclear metalladithiolene complexes based on benzenehexathiol (<i>J. Chem. Soc., Dalton Trans.</i> <b>1998</b>, 2651; <i>Dalton Trans.</i> <b>2009</b>, 1939; <i>Inorg. Chem.</i> <b>2011</b>, <i>50</i>, 6856). Here we report trinuclear complexes with a triphenylene backbone. A reaction with triphenylenehexathiol and group 9 metal precursors in the presence of triethylamine gives rise to trinuclear complexes <b>9</b>–<b>11</b>. The planar structure of <b>11</b> is determined using single crystal X-ray diffraction analysis. The ligand-to-metal charge transfer bands of <b>9</b>–<b>11</b> move to longer wavelengths compared with those of mononuclear <b>12</b>–<b>14</b>. Electrochemical measurements disclose that the one-electron and two-electron reduced mixed-valent states are stabilized thermodynamically. UV–vis–NIR spectroscopy for the reduced species of <b>9</b> identifies intervalence charge transfer bands for <b>9</b>^– and <b>9</b>^2–, substantiating the existence of electronic communication among the three metal nuclei. These observations prove that the triphenylene backbone transmits π-conjugation among the three metalladithiolene units

π‑Conjugated Nickel Bis(dithiolene) Complex Nanosheet

A π-conjugated nanosheet comprising planar nickel bis­(dithiolene) complexes was synthesized by a bottom-up method. A liquid–liquid interfacial reaction using benzenehexathiol in the organic phase and nickel­(II) acetate in the aqueous phase produced a semiconducting bulk material with a thickness of several micrometers. Powder X-ray diffraction analysis revealed that the crystalline portion of the bulk material comprised a staggered stack of nanosheets. A single-layer nanosheet was successfully realized using a gas–liquid interfacial reaction. Atomic force microscopy and scanning tunneling microscopy confirmed that the π-conjugated nanosheet was single-layered. Modulation of the oxidation state of the nanosheet was possible using chemical redox reactions

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 × 10² 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. <i>Nano Lett.</i> <b>2013</b>, <i>13</i>, 2842)