Tetsuya Kambe

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 × 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).

Expanding Family of π-Conjugated Trinuclear Dithiolenes: The Cases of Group 8 (RuII) and 10 (NiII and PtII) Metals

New π-conjugated trinuclear dithiolenes with group 8 (6, Ru(II)) and 10 (7 and 8, Ni(II) and Pt(II)) metals were synthesized. Compounds 6 and 7 exhibited intense electronic communication through the phenylene bridge among the three dithiolene moieties during oxidation of the metalladithiolene rings, which has not been confirmed in the analogous family of group 9 metals, 1-5. Compound 8 exhibited an intense absorption band across the visible and near-IR regions, which was assigned as a charge transfer to the diimine and was red-shifted and broadened compared to the corresponding band of the mononuclear complex.

Ir3Co6 and Co3Fe3 Dithiolene Cluster Complexes: Multiple Metal-Metal Bond Formation and Correlation between Structure and Internuclear Electronic Communication

π-Conjugated trinuclear iridium and cobalt dithiolenes undergo multiple metal-metal bond formation with Co(2)(CO)(8) and Fe(CO)(5), giving rise to Ir(3)Co(6) nonanuclear and Co(3)Fe(3) hexanuclear cluster complexes 5 and 6, respectively. 5 retains a planar framework and intense π conjugation across the three iridadithiolenes and the phenylene bridge, which results in intense electronic communication among the three Co(2)(CO)(5) units in reduced mixed-valent states.

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

Previously, we synthesized π-conjugated trinuclear metalladithiolene complexes based on benzenehexathiol (J. Chem. Soc., Dalton Trans.1998, 2651; Dalton Trans.2009, 1939; Inorg. Chem.2011, 50, 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 9-11. The planar structure of 11 is determined using single crystal X-ray diffraction analysis. The ligand-to-metal charge transfer bands of 9-11 move to longer wavelengths compared with those of mononuclear 12-14. 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 9 identifies intervalence charge transfer bands for 9(-) and 9(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.

A bis(terpyridine)iron network polymer on carbon for a potential energy storage material

A bis(terpyridine)iron network polymer was fabricated by electropolymerisation on a glassy carbon electrode. The modified electrode allowed high-speed charging and discharging with a minor capacity decay (only 5% after 3000 cycles at 1 V s(-1)).

Solution-phase synthesis of Al 13 − using a dendrimer template

Superatoms, clusters that mimic the properties of elements different to those of which they are composed, have the potential to serve as building blocks for unprecedented materials with tunable properties. The development of a method for the solution-phase synthesis of superatoms would be an indispensable achievement for the future progress of this research field. Here we report the fabrication of aluminum clusters in solution using a dendrimer template, producing Al13−, which is the most well-known superatom. The Al13− cluster is identified using mass spectrometry and scanning transmission electron microscopy, and X-ray photoelectron spectroscopy is used to measure the binding energies. The superatomic stability of Al13− is demonstrated by evaluating its tendency toward oxidation. In addition, the synthesis of Al13− in solution enables electrochemical measurements, the results of which suggest oxidation of Al13−. This solution-phase synthesis of Al13− superatoms has a significant role for the experimental development of cluster science.Superatoms—clusters that exhibit some of the properties of elemental atoms—could serve as building blocks for functional materials, but their synthesis outside of the gas phase is highly challenging. Here, the authors use a dendrimer template to successfully produce Al13− in solution.

Reducing Capsule based on Electron Programming: Versatile Synthesizer for Size-controlled Ultra-small Metal Clusters

Controlled reducing capsules with a specific number of reducing electrons were achieved by appropriately placed BH3 units in the dendritic polyphenylazomethines (DPAs). Using the 1:1 coordination fashion on their basic branches with radius affinity gradient, the 4th generation DPA (DPAG4) possessing four BH3 units in the central positions was prepared as a template synthesizer for size-controlled ultra-small metal clusters. This was well-demonstrated by reduction of Ag, Pt, and other metal ions resulting in monodispersed ultra-small clusters.

Bismuth Complexes in Phenylazomethine Dendrimers: Controllable Luminescence and Emission in the Solid State

Dendritic phosphors were obtained by the stepwise integration of BiCl3 in phenylazomethine dendrimers. The bismuth-coordinated phenylazomethines displayed photoluminescence at 500-800 nm, and the intensity could be tuned by changing the stoichiometry of BiCl3 and the dendrimer. This phosphor did not show serious luminescence quenching even though the local concentration of BiCl3 in the dendrimer was as high as 20 M, and luminescence was also observed in the solid state. The absorption and emission properties could be reversibly switched by addition of a Lewis base or under electrochemical redox control, which induced the reversible complexation of BiCl3 in the dendrimer.

Atom-hybridization for synthesis of polymetallic clusters

The chemistry of metal clusters on the sub-nanometer scale is not yet well understood because metal clusters, especially multimetallic clusters, are difficult to synthesize with control over size and composition. The template synthesis of multimetallic sub-nanoclusters is achieved using a phenylazomethine dendrimer as a macromolecular template. Its intramolecular potential gradient allows the precise uptake of metal precursor complexes containing up to eight elements on the template. The usefulness of this method is demonstrated by synthesizing multimetallic sub-nanoclusters composed of five elements (Ga1In1Au3Bi2Sn6). The size and composition of this cluster can be precisely controlled and the metals involved are alloyed with each other. This approach provides the ability to easily blend different metals in various combinations to create new materials on the sub-nanometer scale, which will lead to the development of a new area in the field of chemistry.Multimetallic clusters are difficult to synthesize with control over elemental composition and organization. Here, the authors use dendrimers to precisely template the formation of five-element sub-nanoclusters, providing an elegant route to otherwise-inaccessible multinary compounds.