In the past Naoto Tsutsumi has collaborated on articles with Yonezo Maeda and Tsuyoshi Kiyotsukuri. One of their most recent publications is An unusual example of a rapid spin-equilibrium iron complex. Which was published in journal Chemical Physics Letters.

More information about Naoto Tsutsumi research including statistics on their citations can be found on their Copernicus Academic profile page.

Naoto Tsutsumi's Articles: (9)

An unusual example of a rapid spin-equilibrium iron complex

AbstractBis(N-(1-benzoyl-2-propylidene)-2-pyridylmethylaminato)iron(III) hexafluorophosphate (Fe(bzpa)2PF6 is shown to be a spin-equilibrium compound between low- (S = 12) and high- (S = 52) spin states depending on temperature, and to have the unusual property that the relaxation time of the spin change is shorter than the Mössbauer lifetime (1 × 10−7s) of iron- 57 (l = 32) in the solid state.

Polymer paperCarrier photogeneration of N-phenylcarbazole doped poly(bisphenol A carbonate) film

AbstractThe carrier photogeneration mechanism of N-phenylcarbazole (PhCz) doped poly(bisphenol A carbonate) film with 2,6-dimethyl-p-benzoquinone (MQ) as an electron acceptor was investigated. The carrier generation efficiency, η, was measured by a xerographic technique. The extrinsic carrier generation efficiency, ηe, was calculated from η and fluorescence quenching data. The large increase of ηe with increasing PhCz is attributed to excitation energy migration to the acceptor site MQ. The probability of free carrier formation at the acceptor site, Ae(E), is nearly constant, ≈ 1.5 × 10−3. The electric field dependence of ηe was analysed by an Onsager plot. The initial separation distance of the ion pair, ro is 1.8–2.0 nm. The slight increase of Ae(E) and ro with increasing PhCz concentration seems to be caused by enhanced escape probability from the geminate recombination due to hole migration.

Polymer paperOxygen permeability of silicon-containing network polyamide and copolyamide films

AbstractNetwork polyamide films (EY) of trimesic acid (Y) and 1,3-bis(3-aminopropyl)tetramethyldisiloxane (E), and network copolyamide films (EYEn) of Y and E with aliphatic dicarboxylic acids (n) and those (EY/EE′) of Y and E with 1,3-bis(3-carboxypropyl)tetramethyldisiloxane (E′) were prepared. The prepolymer was prepared using a melt polycondensation method, and then a dimethylformamide solution of the prepolymer was cast on an aluminium plate. The cast film obtained was post-polymerized to form a network structure. Post-polymerized films were flexible, transparent and insoluble in common solvents. The molecular and supramolecular structures of these network polymers were characterized by infra-red absorption spectra, X-ray diffraction analysis, differential thermal analysis and thermomechanical analysis. Oxygen and nitrogen permeabilities increased with increasing temperature. EY homopolymer had PO2 of 4.6 × 10−10 cm3(s.t.p.) cm cm−2 s−1 cmHg−1 and PO2PN2 of 3.4 at 60°C. Incorporation of copolymer components En and EE′ enhanced the oxygen and nitrogen permeabilities while decreasing the glass transition temperature (Tg). The decrease of Tg increased PO2, which may be explained by enhancement of the flexibility of the molecular chain. For the EY/EE′ copolymer, an increase in the EE′ component gave rise to an increase of PO2 and a smaller decrease of PO2PN2. The EY/EE′(1090mol%) film had the highest value of PO2 of 3.2 × 10−9 cm3(s.t.p.) cm cm−2 s−1 cmHg−1 and PO2PN2 of 2.8 at 60°C.

Polymer communicationMeasurement of the internal electric field in a poly(vinylidene fluoride)/poly(methyl methacrylate) blend

AbstractA melt-quenched blend of 80 wt% poly(vinylidene fluoride) (PVDF) and 20 wt% poly(methyl methacrylate) (PMMA) has the β-crystal form of PVDF, which grows larger on annealing at higher temperature. The internal electric field Ei induced by poling in the PVDF/PMMA (8020) blend was measured using the technique of electrochromic peak shift of dye dissolved in the blend. It was found that Ei was of the order of 106 V cm−1 (larger than the poling field), and that Ei was anomalously stable when the sample was annealed at higher temperature, whereas the pyroelectricity decreased above the glass transition temperature. We speculated that the space charge may be related to the anomalous stability of Ei.

Polymer paperPreparation and properties of poly(ethylene terephthalate) copolymers with 2,2-dialkyl-1,3-propanediols

AbstractPoly(ethylene terephthalate) (PET) copolymers were prepared by melt polycondensation of dimethyl terephthalate and excess ethylene glycol with 5–30mol% (in feed) of 1,3-propanediol and 2,2-dialkyl-1,3-propanediols, where the dialkyl groups are dimethyl, diethyl and butyl-ethyl. No significant depression of reduced specific viscosity was observed. The comonomer contents in the copolymers are considerably smaller than those in the feed. The crystallinities and densities of heat-treated films decreased with increasing content of comonomer and length of alkyl side chain in the comonomer. The glass transition temperature (Tg) and melting temperature (Tm) were decreased by the copolymerization, while an increase in the length of the alkyl side chain hardly affected the Tm depression of heat-treated films. Alkali resistance, dyeability and thermal shrinkage were remarkably increased by the incorporation of comonomer having an alkyl side chain.

Photoionization of donor-acceptor complex by the internal electric field in blend of poly(vinylidene fluoride) and poly(methyl methacrylate)

AbstractThis paper presents a measurement of the photocurrent of a poled blend of 80 wt% poly(vinylidene fluoride) (PVDF) and 20 wt% poly(methyl methacrylate) (PMMA) containing 5 wt% N-phenylcarbazole (PhCz) and 1 wt% 2,4,7-trinitro-9-fluorenone (TNF) molecules and a discussion of the photoionization of the PhCz-TNF complex by the internal electric field. The high internal electric field, of the order of 106 V cm−1, created by the preferential orientation of polar PVDF β crystallites assists the photoionization of an ion-pair in the polymer matrix, and thus free photocarrier formation by the internal electric field can be expected. The photocurrent illuminated from the positive poled side corresponds to the absorption spectrum of PhCz, while the photocurrent from the negative poled side has maximum current in the absorption edge of PhCz and no photocurrent activity in the strong absorption region of PhCz below 330 nm. No photocurrent was measured for the unpoled sample. These results imply that the internal electric field induced by poling has a significant role in carrier photogeneration. Furthermore, the optical absorbance due to the charge-transfer complex between PhCz and TNF increased non-linearly with increasing poling field.

Structures induced in polysilane and thin polysilane layer coated polymer films by irradiation of femto-second laser pulse

AbstractWe investigated the structures induced in polysilane and polysilane coated thermoplastic bis-phenol A type epoxy (Epoxy) and poly(methyl methacrylate) (PMMA) films by irradiation of near-infrared (NIR) femto-second laser pulse. Long stripe-shaped structures with approximately 200–400 μm length was induced in polysilane bulk. Thin polysilane layer coated Epoxy and PMMA films showed photo-sensitive effect on the formation of stripe-shaped structures in PMMA and Epoxy, whereas no structures were induced in uncoated PMMA and Epoxy films. An ensemble of stripe-shaped structures worked as a diffraction grating. This photo-sensitive effect has potential application to grating structures in optical polymeric fiber (OPF).

Asymmetric energy transfer and optical diffraction in novel molecular glass with carbazole moiety

AbstractAsymmetric energy transfer and optical diffraction under optically interfered beams was presented in composites with novel star-shaped molecular glass end-caped by carbazole moiety, α,α′,α″-tris-(4-(carbazoryl)-n-hexyloxyphenyl)-1,3,5-triisopropylbenzene (Tris). Composite consisted of Tris as host matrix, 2,4,7-trinitro-9-fluorenone (TNF) as a sensitizer, (S)-(-)-1-(4-nitrophenyl)-2-pyrrolidine-methanol (NPP) as a nonlinear optical dye and either tricresyl phosphate (TCP), n-butyl benzyl phthalate (BBP), diphenyl phthalate (DPP), or dicyclohexyl phthalate (DCP) as a plasticizer. Asymmetric two beam coupling (asymmetric energy transfer) and beam diffraction were achieved with no external field. Glass transition temperature of the composites plays an important role for these phenomena of asymmetric energy transfer and optical diffraction with no external field. Highest net gain coefficient of 59.7 cm−1 with optical gain of 151.3 cm−1 and absorption coefficient of 91.6 cm−1 was obtained for Tris/NPP/DPP/TNF (35/20/40/5) composite. TNF anion produced by laser illumination plays a key role of beam diffraction and asymmetric two beam coupling in the composites.

Spectrally-narrowed emissions from a layered organic transistor equipped with a diffraction grating

AbstractWe propose a construction of an organic light-emitting field-effect transistor for producing spectrally-narrowed emissions (SNEs) under current injection. The device is characterized by the followings: a diffraction grating fabricated within the channel region, homogeneous source and drain electrodes made of a low work-function metal and a layered structure of organic semiconductor materials. The organic layered structure was composed of a p-type crystal and an n-type thin film. The latter film was deposited so as to cover the grating on the channel. We observed SNEs from the device when it was operated by applying square-wave alternating gate voltages. The observed spectra were peaking as a dominant line around 578 nm with a full width at half maximum less than 4 nm.

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