Azulene-Based Donor-Acceptor Systems: Synthesis, Optical, and Electrochemical Properties

First published: 07 Aug 2017We describe the synthesis and properties of azulene-substituted 1,1,4,4-tetracyanobutadienes (AzTCBDs) and heteroazulenyl TCBDs. TCBD derivatives were prepared in good to excellent yields through reaction of the corresponding 1-ethynylazulenes with tetracyanoethylene (TCNE). In contrast, the reaction between propargyl alcohols and the 1-azulenyl group in TCNE generated 2-aminofuran derivatives, which were transformed into 6-aminofulvenes with a 1-azulenyl substituent upon treatment with several amines. The optical and electrochemical properties of the AzTCBDs were clarified by UV/Vis and voltammetry. The AzTCBD derivatives exhibited electrochromism, showing a multi-step color change under electrochemical redox conditions. The multistage redox properties of AzTCBDs could be useful for the development of novel organic electronic materials.ArticleCHEMISTRY-A EUROPEAN JOURNAL. 95(1):16696-16709 (2017)journal articl

Dynamic X-Ray Diffraction Technique for Measuring the Crystal Lattice Response in Semicrystalline Polymers against Mechanical Excitations

Dynamic mechanical and crystallographic features which are associated with mechanical excitations on the bulk specimen of the semicrystalline polymers are generalized on the basis of factors such as mechanical dispersions of orientation of crystallites and deformation of the crystal superstructure. The latter factor may further be divided into inter-lamellae and intra-lamella responses within the superstructure such as spherulite. The present paper describes the theory and techniques set up to observe the intralamella response in the semicrystalline polymers against mechanical excitations by means of a dynamic x-ray diffraction technique. This observation is required to measure the inphase and out-of-phase components of the angular vibration of the diffraction maximum raised by the forced sinusoidal strain of the test specimen. For this purpose, it was shown that a twin detector technique could successfnlly be applicable where the diffraction peak shift was amplified by simultaneous measurements of the shoulder intensities of the diffraction perk at the higher and the lower diffraction angles to the peak maximum

First synthesis of 1-(indo1-2-yl)azulenes by the Vilsmeier-Haack type arylation with triflic anhydride as an activating reagent

Azulene derivatives reacted with 2-indolinones in the presence of triflic anhydride (Tf2O) to afford 1-(indo1-2-yl)azulenes in good yields. In the cases of the reaction of 6-tert-butyl-1-(methylthio)azulene (11) and 1-(1,4-dihydropyridin-4-yl)azulene 14, 1,1'-biazulene derivative 24 and 1-(indo1-2-yl)azulene (2) were obtained under the similar reaction conditions, respectively, instead of the presumed electrophilic substitution products.ArticleTETRAHEDRON LETTERS. 53(12):1493-1496 (2012)journal articl

The influence of decision-making rules on individual preference for ecological restoration: Evidence from an experimental survey

We conduct an experimental survey to analyze how rules for collective decision-making influence individual preferences concerning nature restoration projects. Our study compares two decision-making rules - a consensus rule and a majority rule - wherein participants decide on a plan concerning nature restoration in the Kushiro Wetland, Japan. Our main finding is that the difference between the individual preferences and collective decision-making is less significant under the consensus rule than the majority rule. Furthermore, there is a larger disparity with regard to the marginal willingness to pay between collective and individual decisions when participants are unsatisfied with the results of collective choice.

Information and Export Decisions: Bank’s Role as a Conduit of Information

This paper examines how firms’ decision to start exporting is affected by the availability of information on export markets. Unlike existing studies which focus on information sharing among firms, we are interested in the information provided by firms’ main bank. Specifically, using a unique dataset containing information on both Japanese firms’ export activities and their main banks’ experience in transacting with other exporting firms, we examine whether main banks act as a conduit of information on export markets. We find that information spillovers through main banks positively affect client firms’ decision to start exporting (extensive margin), implying that information on foreign markets provided by banks substantially reduces the fixed entry cost of exporting. On the other hand, we do not find any evidence that information provided by banks has an effect on the export volume or on the growth rate of exports (intensive margin). Our results highlight that channels of information spillovers other than those examined in the literature so far may be of considerable importance

Synthesis of 2-Azulenyl-1,1,4,4-tetracyano-3-ferrocenyl-1,3-butadienes by [2+2] Cycloaddition of (Ferrocenylethynyl)azulenes with Tetracyanoethylene

1-, 2-, and 6-(Ferrocenylethynyl)azulene derivatives 1016 have been prepared by palladium-catalyzed alkynylation of ethynylferrocene with the corresponding haloazulenes under SonogashiraHagihara conditions. Compounds 1016 reacted with tetracyanoethylene (TCNE) in a [2+2] cycloadditioncycloreversion reaction to afford the corresponding 2-azulenyl-1,1,4,4,-tetracyano-3-ferrocenyl-1,3-butadiene chromophores 1723 in excellent yields. The redox behavior of the novel azulene chromophores 1723 was examined by using cyclic voltammetry (CV) and differential pulse voltammetry (DPV), which revealed their multistep electrochemical reduction properties. Moreover, a significant color change was observed by visible spectroscopy under electrochemical reduction conditions.ArticleCHEMISTRY-A EUROPEAN JOURNAL. 19(18):5721-5730 (2013)journal articl

Synthesis of push-pull chromophores by the sequential [2+2] cycloaddition of 1-azulenylbutadiynes with tetracyanoethylene and tetrathiafulvalene

Azulene-substituted butadiynes have been prepared by Cu-mediated cross- and homo-coupling reactions. The azulene-substituted butadiynes reacted with tetracyanoethylene in a formal [2 + 2] cycloaddition reaction to afford the corresponding 1,1,4,4-tetracyanobutadiene chromophores, in excellent yields. Further [2 + 2] cycloaddition with TTF and TCNE gave novel donor-acceptor chromophores and novel azulene-substituted 6,6-dicyanofulvene derivatives.ArticleORGANIC & BIOMOLECULAR CHEMISTRY. 10(41):8308-8313 (2012)journal articl

Über die Entwicklung der Harnblasenanlage bei Meerschweinchenembryonen

Es ist eine anerkannte Theorie, die von Keibel, Felix und anderen aufgestellt wurde, dass sich die Harnblase aus dem Allantoisschenkel entwickelt. Jedoch behaupten Herr Ofuji und Mori neuerdings, dass diese Theorie nicht bei allen Säugetieren anwendbar ist. Daher haben wir unter Leitung von Herrn Prof. J. Shikinami eine Nachprüfung über die Entwicklung der Harnblasenanlage mit Hilfe der Born-Peter'schen Modellierungsmethode angestellt und folgende Ergebnisse erhalten. 1) Bei Meerschweinchenembryonen gehen die Harnblase und primare Harnröhre aus der gleichen Anlage hervor und sind am Beginn der Entwicklung nicht voneinander zu trennen. Wir müssen deswegen von der sog. Keibel'schen gemeinsamen HarnblasenHarnröhreuanlage sprechen. 2) Der Entstehungsvorgang der gemeinsamen Harnblasen- Harnrohrenanlage bei Meerschweinchenembryonen ist dem bei Mäuse- und Rattenembryonen gerade entgegengesetzt. Am Aufbau dieser Anlage beteiligt sich der ganze Allantoisschenkel mit dem kaudalen Abschnitte des Allantoisganges. 3) Beim Embryo von 14mm Sch.-St.-L. zeigt diese Anlage eine dorsoventralwärts abgeplattete Gestalt; das Querschnittbild des mittleren Abschnittes ist hufeisenformig. 4) Beim 17.0mm langen Embryo teilt sich die gemeinsame Harnblasen- Harnröhrenanlage morphologisch in eine spezielle Harnblasenanlage und eine sp. Harnrohrenanlage. In diesem Stadium des Embryos beginnt sich bereits die Muskulatur der sp. Harnblasenanlage zu entwickeln. 5) Beim Embryo von 32.0mm Sch.-St.-L. beträgt der Längsdurchmesser der Harnblasenanlage 1.0mm, der Sagittaldurchmesser 0.94mm und der Frontaldurchmesser 0.68mm. Die epitheliare Blasenwand weist zahlreiche Falten auf und die Muskulatur erscheint in Form von ringförmigen glatten Muskelbündeln, die sich aus dem die Harnblase rings umgebenden, embryonalen Bindegewebe differenzieren. 6) Im allgemeinen zeigt die Harnblase beim 61, 0mm langen Embryo schon eine eigene Gestalt, morphologisch und histologisch, doch ist die Partie des Blasenscheitels noch unvollendet. 7) Die primäre Harnröhre entsteht durch die Aufteilung der gemeinsamen Harnblasen- Harnrohrenanlage ebenso bei Meerschweinchenembryonen wie bei Mäuse- und Rattenembryonen. Im weiteren Verlauf der Entwicklung verlängert sie sich in kraniokaudaler Richtung und bildet so die ganze weibliche Harnrohre beim 46,0mm langen weiblichen Embryo und die Pars prostatica urethrae beim männlichen Embryo von 61,0mm Sch.-St.-L

Synthesis of 1-(pyridyl, quinolyl, and isoquinolyl)azulenes by Reissert-Henze type reaction

Azulene derivatives reacted with N-oxide of several heterocycles in the presence of trifluoromethanesultonic anhydride (Tf(2)O) to afford 1-(pyridyl, quinolyl, and isoquinolyl)azulenes in good yield, respectively. In the case of the reaction with the 1-azulenyl methyl sulfide (12), 1,1'-biazulene derivative 13 was obtained under the similar reaction conditions. The first synthesis of unsymmetrical 1,3-di(pyridyl)azulene derivative was also established via our new preparation method following the electrophilic pyriclinylation using the reaction with pyridine in the presence of Tf(2)O.ArticleTETRAHEDRON LETTERS. 51(39):5127-5130 (2010)journal articl