(Macromolecular Chemistry)
(Macromolecular Chemistry)
(b.1947), B.S. (1970, Waseda), Ph.D.(1975, Waseda), Post. Doc. (1977-1978,
Humboldt Fellow: Berlin Free), Assist. Prof. (1980, Waseda), Assoc. Prof.
(1982, Waseda), Prof. (1987, Waseda), Visit. Prof. (1992, NY Polytech).
Vice-President of the Society of Polymer Science, Japan.
Chairman of Research Group on Macromolecular Complexes, Vice-Chairman of Research Group on Fuel Cell Materials, Japan
The Award of the Society of Polymer Science, Japan (1990).
keywords
Functional Polymer / Conjugated Polymer / Magnetic Polymer / Metalloporphyrin / Macromolecular Complex / Oxygen Carrier / Air Separation Membrane
Room 65-303
3-4-1 Okubo, Shinjuku-ku, Tokyo 169-8555, Japan
Tel: +81-3-5286-3214, +81-3-3200-2669
Fax: +81-3-3209-5522
E-mail: nishide@waseda.jp
Research Interests
Investigation of syntheses and new performances of highly-designed ,ƒÎ-conjugated polymers.
Purely organic-derived radical polymers are a new class of molecules that are relevant to the future frontier of electronic and magnetic functions. Organic radical polymers bear multi-unpaired electrons, and are usually chemically reactive. However, they could be converted into stable materials by designing their molecular structures.
Very high-spin and durable organic polymers are realized for the ƒÎ-conjugated polymers bearing pendant radical groups which are bonded with the backbone to satisfy a ferromagnetic connectivity. A typical example is the poly(2-radical substituted -1,4-phenylenevinylene) . A restricted head-to-tail linkage in the polymer leads to the high-spin polymer. Because the exchange interaction between electron spins through the ƒÎ-conjugated system is very strong, this macromolecular approach has a potential for obtaining interesting magnetic properties even at room temperature. Magnetic force microscopy of the nanometer-sized, high-spin and hyperbranched polymer revealed a magnetic response exactly on the molecular position with its molecular size and spin density . The single-molecular based magnetic image is now being examined as a nano-scaled molecular magnet.
These radical polymers display a reversible and very rapid redox activity, which enables both a high energy-density and power-rate property for application as an electrode-active material in batteries. The radical polymers are also applicable as a hole-transporting layer in organic EL devices.
Red-colored membranes having a selective, reversible, and hemoglobin-like
oxygen-binding capacity are prepared by complexing cobaltporphyrins with
polymers . Oxygen transport is facilitated in the solid-state membranes
. A downstream oxygen concentration of >90% was obtained after only
a single pass of air through the membrane.
Green chemical polymerization to form poly(phenylene oxide)s and new proton-conducting polymers are also being studied.
Representative Publications
(1) "Oxidative Polymerization of 2,6-Dimethylphenol to Form Poly(2,6-dimethyl-1,4-phenyleneoxide) in Water", Angew. Chem. Int. Ed., 43, 730-733 (2004).
(2) "A High-Spin and Durable Polyradical: Poly(4- dianisylaminium-1,2-phenylenevinylene)", J. Org. Chem., 69, 631-638 (2004).
(3) "Ladderlike Ferromagnetic Spin Coupling Network on a -Conjugated Pendant Polyradical", J. Amer. Chem. Soc., 125, 3554-3557 (2003).
(4) "Facilitated Oxygen Transport Membranes of Picket-fence Cobaltporphyrin Complexed with Various Polymer Matrixes", Ind. Eng. Chem. Res., 42, 5954-5958 (2003).
(5) "Depolymerization of Poly(2,6-dimethyl-1,4- phenylene oxide) under Oxidative Conditions", Chem. Eur. J., 9, 4240-4246 (2003).
(6) "A Duplex of Tetra(2-pyridyl)porphyrin and Tetra- hydroxylcalix[4]arene", Chem. Lett., 32, 1052-1053 (2003).
(7) "m-Phenylene-Linked Aromatic Poly(aminium cation radical)s: Persistent High-Spin Organic Polyradicals", Org. Lett., 5, 2165-2168 (2003).
(8) "Tetrakis[o-(N-methyl)pyridinium]porphyrin Ensembles with Coordinated Cyclodextrin- Penetrating Phenethylimidazole: Reversible Dioxygen- Binding in Aqueous Solution", Chem. Commun., 50-51 (2003).
(9) "Magnetic Force Microscopic Images of Nanometer-Sized Polyradical Particles", Polymer J., 35, 71-75 (2003).
(10) "Hyperbranched Poly(phenylenevinylene) Bearing Pendant Phenoxys for a High-Spin Alignment", J. Mater. Chem., 12, 3578-3584 (2002).
(11) "Poly(1,2-phenylenevinylene) Ferromagnetically 3,5-Bearing Phenoxyl Radicals", Macromolecules, 35, 690-698 (2002).
(12) "A Novel Triphenylamine-Substitued Poly(p- phenylenevinylene): Improved Photo- and Electroluminescent Properties", Chem. Mater., 13, 3817-3819 (2001).
(13) "A Nanometer-Sized High-Spin Polyradical: Poly(4-phenyl-1,2-phenylenevinylene) Planarily Extended in a Non-Kekule Fashion and Its Magnetic Force Microscopic Images", J. Amer. Chem. Soc., 123, 5942-5946 (2001).
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