Masakazu Yamagishi

Linear- and Angular-Shaped Naphthodithiophenes: Selective Synthesis, Properties, and Application to Organic Field-Effect Transistors

A straightforward synthetic approach that exploits linear- and angular-shaped naphthodithiophenes (NDTs) being potential as new core structures for organic semiconductors is described. The newly established synthetic procedure involves two important steps; one is the chemoselective Sonogashira coupling reaction on the trifluoromethanesulfonyloxy site over the bromine site enabling selective formation of o-bromoethynylbenzene substructures on the naphthalene core, and the other is a facile ring closing reaction of fused-thiophene rings from the o-bromoethynylbenzene substructures. As a result, three isomeric NDTs, naphtho[2,3-b:6,7-b]dithiophene, naphtho[2,3-b:7,6-b]dithiophenes, and naphtho[2,1-b:6,5-b]dithiophene, are selectively synthesized. Electrochemical and optical measurements of the parent NDTs indicated that the shape of the molecules plays an important role in determining the electronic structure of the compounds; the linear-shaped NDTs formally isoelectronic with naphthacene have lower oxidation potentials and more red-shifted absorption bands than those of the angular-shaped NDTs isoelectronic with chrysene. On the contrary, the performance of the thin-film-based field-effect transistors (FETs) using the dioctyl or diphenyl derivatives were much influenced by the symmetry of the molecules; centrosymmetric derivatives tend to give higher mobility (up to 1.5 cm(2) V(-1) s(-1)) than axisymmetric ones (∼0.06 cm(2) V(-1) s(-1)), implying that the intermolecular orbital overlap in the solid state is influenced by the symmetry of the molecules. These results indicate that the present NDT cores, in particular the linear-shaped, centrosymmetric naphtho[2,3-b:6,7-b]dithiophene, are promising building blocks for the development of organic semiconducting materials.

Direct Observation of Lanthanide(III)-Phthalocyanine Molecules on Au(111) by Using Scanning Tunneling Microscopy and Scanning Tunneling Spectroscopy and Thin-Film Field-Effect Transistor Properties of Tb(III)- and Dy(III)-Phthalocyanine Molecules

The crystal structures of double-decker single molecule magnets (SMM) LnPc(2) (Ln = Tb(III) and Dy(III); Pc = phthalocyanine) and non-SMM YPc(2) were determined by using X-ray diffraction analysis. The compounds are isomorphous to each other. The compounds have metal centers (M = Tb(3+), Dy(3+), and Y(3+)) sandwiched by two Pc ligands via eight isoindole-nitrogen atoms in a square-antiprism fashion. The twist angle between the two Pc ligands is 41.4 degrees. Scanning tunneling microscopy was used to investigate the compounds adsorbed on a Au(111) surface, deposited by using the thermal evaporation in ultrahigh vacuum. Both MPc(2) with eight lobes and MPc with four lobes, which has lost one Pc ligand, were observed. In the scanning tunneling spectroscopy images of TbPc molecules at 4.8 K, a Kondo peak with a Kondo temperature (T(K)) of approximately 250 K was observed near the Fermi level (V = 0 V). On the other hand, DyPc, YPc, and MPc(2) exhibited no Kondo peak. To understand the observed Kondo effect, the energy splitting of sublevels in a crystal field should be taken into consideration. As the next step in our studies on the SMM/Kondo effect in Tb-Pc derivatives, we investigated the electronic transport properties of Ln-Pc molecules as the active layer in top- and bottom-contact thin-film organic field effect transistor devices. Tb-Pc molecule devices exhibit p-type semiconducting properties with a hole mobility (mu(H)) of approximately 10(-4) cm(2) V(-1) s(-1). Interestingly, the Dy-Pc based devices exhibited ambipolar semiconducting properties with an electron mobility (mu(e)) of approximately 10(-5) and a mu(H) of approximately 10(-4) cm(2) V(-1) s(-1). This behavior has important implications for the electronic structure of the molecules.

V‐Shaped Organic Semiconductors With Solution Processability, High Mobility, and High Thermal Durability

V-shaped organic semiconductors have been designed and synthesized via a large-scale applicable synthetic route. Solution-crystallized films based on such molecules have demonstrated high-performance transistor properties with maximum mobilities of up to 9.5 cm(2) V(-1) s(-1) as well as pronounced thermal durability of up to 150 °C inherent in the V-shaped cores.

High‐Performance Solution‐Processable N‐Shaped Organic Semiconducting Materials with Stabilized Crystal Phase

N-shaped organic semiconductors are synthesized via four steps from a readily available starting material. Such semiconductors exhibit preferable ionization potential for p-type operation, thermally stable crystalline phase over 200 °C, and high carrier mobility up to 16 cm(2) V(-1) s(-1) (12.1 cm(2) V(-1) s(-1) on average) with small threshold voltages in solution-crystallized field-effect transistors.

Inch-Size Solution-Processed Single-Crystalline Films of High-Mobility Organic Semiconductors

A method for continuously growing large-domain organic semiconductor crystals is developed to fabricate multi-array high-mobility organic transistors. An organic semiconductor solution is held at the edge of a moving blade to grow a large-area crystalline thin film. The continuous evaporation of the solvent at around 100 °C, while the solution is supplied at the same rate, allows the organic crystals to grow steadily on the substrate to several inches in size. The performance of the arrays of field-effect transistors based on the large-domain crystal films is excellent, with mobility of 5–10 cm2 V-1 s-1.

Reduction of prostacyclin synthesis as a possible cause of transient flow reduction in a partially constricted canine coronary artery.

Coronary blood flow decreases cyclically in a partially occluded coronary artery of anesthetized dogs. Spontaneous aggregation and deaggregation of platelet plugs in the constricted artery have been indicated to be responsible for this phenomenon. A current hypothesis is that platelet aggregation may be determined by a balance between proaggregatory platelet product, thromboxane A2 (TXA2), and antiaggregatory substance, prostacyclin (PGI2). To elucidate the relationship between the cyclical reduction of coronary flow (CRCF) and metabolic alterations of TXA2 and PGI2, we attempted to determine the plasma levels of their stable catabolites, thromboxane B2 (TXB2) and 6-keto-prostaglandin F1 alpha (6-keto-PGF1 alpha), in the coronary circulation of 69 dogs. Of 40 cases, 20 cases exhibited CRCF accompanying a significant increase in TXB2 in the coronary sinus (CS) (P less than 0.05) and constant levels of 6-keto-PGF1 alpha in the CS and aorta (Ao). Another 20 cases did not exhibit CRCF that accompanied a marked increase in 6-keto-PGF1 alpha (P less than 0.05) with virtually no change in TXB2 in the CS and Ao. A higher dose of indomethacin (10 mg/kg, i.v.) was capable of evoking CRCF in cases not exhibiting CRCF spontaneously. Under these conditions, a significant decrease in 6-keto-PGF1 alpha was seen both in the CS and Ao compared with lower doses of indomethacin (1 to 3 mg/kg, P less than 0.01), that produced less pronounced reduction of 6-keto-PGF1 alpha without CRCF. Intravenous infusion of PGI2 (0.1 microgram/kg/min.) completely abolished spontaneously and indomethacin-induced CRCF with a marked elevation of 6-keto-PGF1 alpha in the CS and Ao. Although OKY-1580, a TXA2 synthetase inhibitor, relieved spontaneously-evoked CRCF with a marked increase in 6-keto-PGF1 alpha and a slight reduction of TXB2, indomethacin-induced CRCF was not abolished by this agent. These results are consistent with the hypothesis that the reduction of endogenous PGI2 synthesis in the vascular wall is related to the occurrence of CRCF after partial constriction of coronary artery and indomethacin.

Boron-Stabilized Planar Neutral π-Radicals with Well-Balanced Ambipolar Charge-Transport Properties

Organic neutral π-monoradicals are promising semiconductors with balanced ambipolar carrier-transport abilities, which arise from virtually identical spatial distribution of their singly occupied and unoccupied molecular orbitals, SOMO(α) and SOMO(β), respectively. Herein, we disclose a boron-stabilized triphenylmethyl radical that shows outstanding thermal stability and resistance toward atmospheric conditions due to the substantial spin delocalization. The radical is used to fabricate organic Mott-insulator transistors that operate at room temperature, wherein the radical exhibits well-balanced ambipolar carrier transport properties.

High performance oxygen-bridged N-shaped semiconductors with a stabilized crystal phase and blue luminescence

Here, we describe an oxygen-bridged N-shaped π-electron core, dinaphtho[2,3-d:2′,3′-d′]benzo[1,2-b:4,5-b′]difuran (DNBDF), as a new entity of organic semiconducting materials. Interestingly, by introduction of flexible alkyl chains at appropriate positions, DNBDF π-cores exhibit solution processability, a highly stabilized crystal phase, high mobility, and blue luminescence as a solid.