有機(多)金属反応剤の環化反応による多環芳香族炭化水素の新規合成法に関する研究

京都大学0048新制・課程博士博士(工学)甲第16095号工博第3418号新制||工||1516(附属図書館)28674京都大学大学院工学研究科材料化学専攻(主査)教授 松原 誠二郎, 教授 赤木 和夫, 教授 杉野目 道紀学位規則第4条第1項該当Doctor of Philosophy (Engineering)Kyoto UniversityDA

Palladium-catalyzed double cross-coupling reaction of 1,2-bis(pinacolatoboryl)alkenes and -arenes with 2,2′-dibromobiaryls: annulative approach to functionalized polycyclic aromatic hydrocarbons

This study demonstrates that the double cross-coupling reaction of 1, 2-bis(pinacolatoboryl)alkenes and -arenes with 2, 2′-dibromobiaryls proceeds smoothly with the aid of a catalytic amount of Pd(PPh3)4 in the presence of excess base to give a variety of polycyclic aromatic hydrocarbons, such as phenanthrenes, [5]helicene, dithienobenzenes, triphenylenes, dibenzo[g, p]chrysenes, and triphenyleno[1, 2-b:4, 3-b′]dithiophenes in good to high yields. It is noteworthy that the annulations using 2, 2′-dibromooctafluorobiphenyl as an electrophile furnish the otherwise difficult to synthesize octafluorophenanthrenes and semi-fluorinated dibenzo[g, p]chrysenes in high yields

Rapid Suzuki-Miyaura Couplings with ppm Level of Palladium Catalyst in a High-Pressure and High-Temperature Water System

A microflow process was developed for Suzuki-Miyaura Couplings (SMCs) in high-pressure and high-temperature (HPHT) water with a small amount of ethanol. Using this approach, an efficient SMC between 4-methylphenylboronic acid and iodobenzene as a model reaction was demonstrated in water medium, in the presence of ppm order PdCl2/NaOH as a simple catalyst/base without any additional ligands, affording the desired products in good yields within <25 s of residence time. The strategy developed for SMCs also demonstrated an aspect of separation by quantitative tracing of 0.1 ppm contaminated Pd with the product, which might be attributed to the low catalyst amount along with the reaction conditions, as well as the immediate membrane separation applied in the sequence

Silaindacenodithiophene-Based Molecular Donor: Morphological Features and Use in the Fabrication of Compositionally Tolerant, High-Efficiency Bulk Heterojunction Solar Cells

A novel solution-processable small molecule, namely, benzo[1,2-b:4,5-b]bis(4,4'-dihexyl-4H-silolo[3,2-b]-thiophene-2,2'-diyl)bis(6-fluoro-4-(5'-hexyl-[2,2'-bithiophene]-5-yl)benzo[c][1,2,5]thiadiazole (p-SIDT(FBTTh2)(2)), was designed and synthesized by utilizing the silaindacenodithiophene (SIDT) framework as the central D-2 donor unit within the D(1)AD(2)AD(1) chromophore configuration. Relative to the widely studied 7,7'-[4,4-bis(2-ethylhexyl)-4H-silolo[3,2-b:4,5-b']dithiophene-2,6-diyl]bis [6-fluoro-4-(5'-hexyl-[2,2 '-bithiophene]-5-yl)benzo[c][1,2,5]thiadiazole] (p-DTS(FBTTh2)(2)), which contains the stronger donor fragment clithienosilole (DTS) as D-2, one finds that p-SIDT(FBTTh2)(2) exhibits a wider band gap and can be used to fabricate bulk heterojunction solar cells with higher open circuit voltage (0.91 V). Most remarkably, thin films comprising p-SIDT(FBTTh2)(2) can achieve exceptional levels of self-organization directly via solution deposition. For example, high-resolution transmission electron microscopy analysis shows that p-SIDT(FBTTh2)(2) spin-cast from chlorobenzene organizes into crystalline domains with lattice planes that extend over length scales on the order of hundreds of nanometers. Such features suggest liquid crystalline properties during the evolution of the film. Moreover, grazing incidence wide-angle X-ray scattering analysis shows a strong tendency for the molecules to exist with a strong "face-on" orientation relative to the substrate plane. Similar structural features, albeit of more restricted dimensions, can be observed within p-SIDT(FBTTh2)(2):PC7IBM bulk heterojunction thin films when the films are processed with 0.4% diiodooctane (DIO) solvent additive. DIO use also increases the solar cell power conversion efficiencies (PCEs) from 1.7% to 6.4%. Of significance from a practical device fabrication perspective is that, for p-SIDT(FBTTh2)(2):PC71BM blends, there is a wide range of compositions (from 20:80 to 70:30 p-SIDT(FBTTh2)(2):PC71BM) that provide good photovoltaic response, i.e., PCE = 4-6%, indicating a robust tendency to form the necessary continuous phases for charge carrier collection. Light intensity photocurrent measurements, charge selective diode fabrication, and internal quantum efficiency determinations were carried out to obtain insight into the mechanism of device operation. Inclusion of DIO in the casting solution results in films that exhibit much lower photocurrent dependence on voltage and a concomitant increase in fill factor. At the optimum blend ratio, devices show high charge carrier mobilities, while mismatched hole and electron mobilities in blends with high or low donor content result in reduced fill factors and device performance