A doubly 2,6-pyridylene-bridged porphyrin-perylene-porphyrin triad.

A doubly 2, 6-pyridylene-bridged porphyrin-perylene-porphyrin triad was synthesized via Suzuki-Miyaura cross coupling reaction, which captures a tetrakis(3-pyridyl)porphyrin guest in a 2 : 1 manner to form a supramolecular complex that undergoes photo-induced electron transfer

Аналіз передумов формування регіональної конкурентоспроможності в соціально-економічній сфері

У статті здійснено аналіз основних чинників, що зумовлюють необхідність вирішення нагальних питань у сфері соціально-економічного розвитку вітчизняних регіонів. Детально прокоментовано основні показники соціально-економічного розвитку в Україні. Визначено проблеми української економіки, що зумовлені зокрема недосконалістю розвитку та підтримки соціальної складової. Зазначено переваги від формування стратегії соціально-економічного розвитку держави на регіональному рівні. Запропоновано актуальні напрями реалізації регіональних проектів у соціальній сфері.В статье проанализированы основные факторы, которые обусловливают необходимость решения современных проблем в сфере социально-экономического развития отечественных регионов. Детально прокомментированы основные показатели социально-экономического развития в Украине. Определены проблемы украинской экономики, которые обусловлены в частности несовершенством развития и поддержки социальной составляющей. Определены преимущества от формирования стратегии социально-экономического развития государства на региональном уровне. Предложены актуальные направления реализации региональных проектов в социальной сфере.The article analyzes the main factors that contribute to the need to solute urgent issues in the sphere of social and economic development of regions. It is commented in detail the main indicators of social and economic development in Ukraine. The problems of the Ukrainian economy caused by imperfections including development and maintenance of the social component are identified. The benefits from the formation of social and economic development at the regional level are indicated. Directions of regional projects realization in the social sphere are proposed. Modern regional development of Ukraine confirms spread of negative trends such as deepening of regional disparities, worsening of social and economic problems of the regions due to lack of effective system of implementation of the state regional policy in social and economic sphere. It is necessary to regulate regional development of Ukraine with strengthening of effective factors through qualitative use of decentralization of power due to reduced direct financial assistance and the use of preferences and guarantees. The main areas of regional projects implementation in the social sphere should be: creating long-term plan of infrastructure development in the regions; joint development of communal medical network, wellness and spa and other facilities of social purpose with departmental, business and private funding. There are such advantages of forming a strategy of social and economic potential of the state at the regional level: the needs of the region is best known for stakeholders (regional governments, businesses, NGOs, local communities); definition of strategic directions of development at the regional level encourages businesses, organizations, non-profit sector, local communities in the process of regional governance; promoting decentralized management processes; the possibility of optimal coordination of local interests with regional and so on

On-surface synthesis and characterization of nitrogen-substituted undecacenes

Heteroatom substitution in acenes allows tailoring of their remarkable electronic properties, expected to include spin-polarization and magnetism for larger members of the acene family. Here, we present a strategy for the on-surface synthesis of three undecacene analogs substituted with four nitrogen atoms on an Au(111) substrate, by employing specifically designed diethano-bridged precursors. A similarly designed precursor is used to synthesize the pristine undecacene molecule. By comparing experimental features of scanning probe microscopy with ab initio simulations, we demonstrate that the ground state of the synthesized tetraazaundecacene has considerable open-shell character on Au(111). Additionally, we demonstrate that the electronegative nitrogen atoms induce a considerable shift in energy level alignment compared to the pristine undecacene, and that the introduction of hydro-aza groups causes local anti-aromaticity in the synthesized compounds. Our work provides access to the precise fabrication of nitrogen-substituted acenes and their analogs, potential building-blocks of organic electronics and spintronics, and a rich playground to explore π-electron correlation

メゾ - メゾ ケツゴウ ポルフィリン タリョウタイ ノ カガク

京都大学0048新制・論文博士博士(理学)乙第11621号論理博第1459号新制||理||1439(附属図書館)UT51-2005-D539(主査)教授 大須賀 篤弘, 教授 林 民生, 教授 丸岡 啓二学位規則第4条第2項該当Doctor of ScienceKyoto UniversityDFA

A β-to-β 2,5-thienylene-bridged cyclic porphyrin tetramer: its rational synthesis and 1 : 2 binding mode with C60

A β-to-β 2, 5-thienylene-bridged cyclic porphyrin tetramer was rationally synthesized via a concise synthetic route. The tetraporphyrin exhibits a positive cooperative binding ability to C60 and demonstrates a new potential of the nonplanar, distorted cyclic porphyrin arrays

Synthesis and Morphological Control of Organic Semiconducting Materials Using the Precursor Approach

Pristine π-extended aromatic compounds are attractive as organic functional materials including organic semiconductors, but are difficult to synthesize in pure form because of their low solubility in common organic solvents. The precursor approach is a very useful method to synthesize pure π-extended aromatic compounds that cannot be prepared via traditional organic synthesis in flasks. In this approach, pure precursors are first prepared; these precursors are then converted quantitatively to the target molecules via a retro-Diels–Alder reaction or Strating–Zwanenburg photodecarbonylation reaction. This approach has also been used for the on-surface synthesis of the large acenes, heptacene and nonacene, under ultra-high vacuum in order to investigate their electronic properties, and is useful for the control of the packing structure of organic semiconductors in solution–processed films. The charge carrier mobilities of organic photovoltaics and organic field effect transistors have been improved using the precursor approach in combination with substituent effects. This account focuses on the synthesis and morphological control of aromatic compounds using the precursor approach in our group in the last decade

Semiconducting Self-Assembled Nanofibers Prepared from Photostable Octafluorinated Bisanthene Derivatives

Bisanthene is an important class of small two-dimensional polycyclic aromatic hydrocarbons with a zigzag-edged graphene nanoribbon character. Therefore, the functionalization and deep understanding of the structure-property relationship of bisanthene would provide an effective design for small organic molecular devices. In this study, octa- and tetrafluorinated bisanthene derivatives were synthesized for investigating the effect of electronegative fluorine substitution on the structure and physical property of bisanthene. Firstly, the octafluorinated bisanthene derivative has a twisted structure due to the steric repulsion of fluorine atoms at the bay region. Secondly, the absorption and fluorescence peak maxima are blueshifted with an increase in the degree of fluorine substitution. Notably, a triisopropylsilylethynyl-substituted octafluorinated derivative (F8) exhibited strong fluorescence at 657 nm with high fluorescence quantum yield (84%). Additionally, cyclic voltammograms indicate the positive effect of fluorine substitution on the high highest occupied molecular orbital energy level of the molecules; thus, F8 molecule exhibited a remarkably increased photostability. Finally, the self-assembled behavior of fluorinated compounds was investigated by scanning electron microscopy and X-ray diffraction analysis. Specifically, F8 self-assembled to form bundles of long semicrystalline nanofibers exhibiting hole-transporting properties (3.4×10-3 cm2 V-1 s-1)

Contraction of π-Conjugated Rings upon Oxidation from Cyclooctatetraene to Benzene via the Tropylium Cation

We have serendipitously discovered a unique transformation of a cyclooctatetraene derivative 1 into a cycloheptatriene spirolactone 3 upon oxidation, which is the first such transformation reported in 60 years. Product 3 could be reversibly interconverted into the aromatic tropylium cation 3H+ by acid/base treatment, which was accompanied by drastic spectroscopic changes. The resultant cycloheptatriene could be further converted into benzene upon oxidation. We characterized all the key structures by X-ray studies. Eventually, the π-conjugated ring size shrinks from 8 to 7, then finally to 6 upon oxidation, in the direction of the stronger aromatization