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Metal–Organic Frameworks and Self-Assembled Supramolecular Coordination Complexes: Comparing and Contrasting the Design, Synthesis, and Functionality of Metal–Organic Materials

Double-decker phthalocyanine complexes with Tb3+ or Dy3+ showed slow magnetization relaxation as a single-molecular property. The temperature ranges in which the behavior was observed were far higher than that of the transition-metal-cluster single-molecule magnets (SMMs). The significant temperature rise results from a mechanism in the relaxation process different from that in the transition-metal-cluster SMMs. The effective energy barrier for reversal of the magnetic moment is determined by the ligand field around a lanthanide ion, which gives the lowest degenerate substate a large |Jz| value and large energy separations from the rest of the substates in the ground-state multiplets.

Lanthanide Double-Decker Complexes Functioning as Magnets at the Single-Molecular Level

The future of energy supply depends on innovative breakthroughs regarding the design of cheap, sustainable, and efficient systems for the conversion and storage of renewable energy sources, such as solar energy. The production of hydrogen, a fuel with remarkable properties, through sunlight-driven water splitting appears to be a promising and appealing solution. While the active sites of enzymes involved in the overall water-splitting process in natural systems, namely hydrogenases and photosystem II, use iron, nickel, and manganese ions, cobalt has emerged in the past five years as the most versatile non-noble metal for the development of synthetic H(2)- and O(2)-evolving catalysts. Such catalysts can be further coupled with photosensitizers to generate photocatalytic systems for light-induced hydrogen evolution from water.

Splitting water with cobalt.

Most associate liquid crystals with their everyday use in laptop computers, mobile phones, digital cameras, and other electronic devices. However, in contrast to their rodlike (calamitic) counterparts, first described in 1907 by Vorlander, disklike (discotic, columnar) liquid crystals, which were discovered in 1977 by Chandrasekhar et al., offer further applications as a result of their orientation in the columnar mesophase, making them ideal candidates for molecular wires in various optical and electronic devices such as photocopiers, laser printers, photovoltaic cells, light-emitting diodes, field-effect transistors, and holographic data storage. Beginning with an overview of the various mesophases and characterization methods, this Review will focus on the major classes of columnar mesogens rather than presenting a library of columnar liquid crystals. Emphasis will be given to efficient synthetic procedures, and relevant mesomorphic and physical properties. Finally, some applications and perspectives in materials science and molecular electronics will be discussed.

Discotic Liquid Crystals: From Tailor-Made Synthesis to Plastic Electronics

Molecular Catalysts for Water Oxidation

An organic photoelectrode working in the water phase : Visible-light-induced dioxygen evolution by a perylene derivative/cobalt phthalocyanine bilayer

Inter-ring overlap integrals in dimer complexes of phthalocyanines and porphyrins

This paper describes the cyclotrimerization reaction of di(2-azulenyl)acetylenes (2a,b) catalyzed by Co2(CO)8 to produce hexa(2-azulenyl)benzene derivatives (1a,b). The cyclooligomerization of 2a and 2b utilizing CpCo(CO)2 as a catalyst produced (η5-cyclopentadienyl)[tetra(2-azulenyl)cyclobutadiene]cobalt complexes (3a,b). The redox behavior of hexakis(6-octyl-2-azulenyl)benzene (1b), bis(6-octyl-2-azulenyl)acetylene (2b), and the cobalt complexes 3a and 3b along with 6-octyl-2-phenylazulene (19) was examined by cyclic voltammetry (CV). The reduction of compound 1b exhibited multiple-electron transfers in one step upon CV with a reduction potential similar to that of compound 19. However, the CVs of compounds 2b, 3a, and 3b were characterized by stepwise waves because of the reduction of each azulene ring. The mesomorphic behaviors of 1b, 2b, and 19 were also studied by differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and X-ray diffraction (XRD) techniques. A new series of azu...

Synthesis and properties of hexakis(6-octyl-2-azulenyl)benzene as a multielectron redox system with liquid crystalline behavior.

An analysis of paramagnetic shifts in proton NMR spectra of non-radical lanthanide(III)-phthalocyanine sandwich complexes

Preparation of azulenyllithium and magnesium reagents utilizing halogen–metal exchange reaction of several iodoazulenes with organolithium or magnesium ate complex

Akio Tajiri

Papers

An organic photoelectrode working in the water phase : Visible-light-induced dioxygen evolution by a perylene derivative/cobalt phthalocyanine bilayer

Inter-ring overlap integrals in dimer complexes of phthalocyanines and porphyrins

Synthesis and properties of hexakis(6-octyl-2-azulenyl)benzene as a multielectron redox system with liquid crystalline behavior.

An analysis of paramagnetic shifts in proton NMR spectra of non-radical lanthanide(III)-phthalocyanine sandwich complexes

Preparation of azulenyllithium and magnesium reagents utilizing halogen–metal exchange reaction of several iodoazulenes with organolithium or magnesium ate complex