Чисельне моделювання фазових переходів у просторово-розподілених стохастичних системах

У рамках комп’ютерного експерименту у роботі вивчалася можливість реалізації фазового переходу типу порушення симетрії у просторово-розподіленій синергетичній системі за рахунок дії скорельованих у часі шумів. У якості базової моделі була використана система Лоренца із двома шумами та просторовою (дифузійною) складовою у рівнянні на параметр порядку. Побудована модель добре описує ряд процесів, наприклад, самоорганізацію дефектної структури під впливом скорельованих внутрішнього та зовнішнього шумів

Problematika Permohonan Grasi Menurut Undang-undang Nomor 22 Tahun 2002

According to executor attorney opinion, no time limit for application clemency, it wills be performing deep constraint on dead punishment execution. Execution of dead punishment also constraint by rule that allows criminal to propose the second clemency application. This constraint still is added by condition that second clemency application is two years of first clemency rejection. Meanwhile according to criminal lawyer reception, with no rule upon, constitute a advantage by criminal dead, since it can propose clemency without time limit for first clemency application and also second application, so execution could be delayed. At Yogyakarta court since year 2002 until now there is no criminal propose clemencies. It is caused, firstly, certain verdict type that could be requested for clemency, secondary by apply clemency cause dead sentence is no postpone except for dead verdict, thirdly most criminal on narcotic and drug abuse case was pleased with first grade verdict

La fundación de la Madrasa al-Adāb por la Asociación de ulemas musulmanes argelinos en la ciudad de Hennaya (Tremecén) en 1950

A biphenyl-fused BODIPY was synthesized through a facile oxidative cyclization of peripheral aryl-substituents at the β-position of the BODIPY unit. The extended π-system of the fused BODIPY induces near-infrared (NIR) absorption and strong π–π interactions in the solid state. These features are beneficial for the application of the dye as a functional material. The biphenyl-fused BODIPY dye was demonstrated to exhibit photocurrent conversion ability on the basis of its <i>n</i>-type semiconducting property

Anion Exchange of Li⁺@C₆₀ Salt for Improved Solubility

<div><p>Anion exchange of [Li⁺@C₆₀]PF₆⁻ salt was performed to obtain three highly soluble Li⁺@C₆₀ salts, namely, the trifluoromethanesulfonate (OTf⁻), bis(trifluoromethylsulfonyl)imide (NTf₂⁻), and tetrakis{3,5-bis(trifluoromethyl)phenyl}borate (TFPB⁻). We investigated the solubility of [Li⁺@C₆₀]OTf⁻, [Li⁺@C₆₀]NTf₂⁻, and [Li⁺@C₆₀]TFPB⁻ and found that, compared with [Li⁺@C₆₀]PF₆⁻, the NTf₂ and TFPB salts had substantially higher solubility. X-ray crystal structure analysis of the TFPB salt revealed that the Li⁺@C₆₀ units spaced further apart because of the large anions in the crystal packing. We attribute the improved solubility of the salts to primarily the increased inter-fullerene distance of the Li⁺@C₆₀ cations. </p> </div

Synthesis of Tetradeca- and Pentadeca(organo)[60]fullerenes Containing Unique Photo- and Electroluminescent π‑Conjugated Systems

Dianions of deca­(phenyl)[60]­fullerene–bis­(cyclopentadienyl ruthenium) complex, (C₆₀Ph₁₀)­(RuCp)₂ (<b>1a</b>), and dimethylated deca­(phenyl)[60]­fullerene, C₆₀Ph₁₀Me₂ (<b>1b</b>), reacted with benzyl bromide to produce [C₆₀Ph₁₀(CH₂Ph₂)₂]­(RuCp)₂ (<b>3a</b> and <b>4a</b>) and tetradeca­(organo)[60]­fullerenes C₆₀Ph₁₀(CH₂Ph₂)₂Me₂ (<b>3b</b> and <b>4b</b>), respectively (Compounds <b>3</b> and <b>4</b> refer to <i>C</i>_2<i>v</i> and <i>C</i>₁ symmetric compounds, respectively.). Nucleophilic addition of benzylmagnesium chloride with the <i>C</i>₁ symmetric compounds <b>4a</b> and <b>4b</b> yielded [C₆₀Ph₁₀(CH₂Ph₂)₃H]­(RuCp)₂ (<b>5a</b>) and pentadeca­(organo)[60]­fullerenes C₆₀Ph₁₀(CH₂Ph₂)₃Me₂H (<b>5b</b>), respectively. Products were structurally characterized by X-ray crystallographic analysis of diruthenium complexes <b>3a</b>, <b>4a</b>, and <b>5a</b>. These X-ray studies revealed that compounds <b>3</b>, <b>4</b>, and <b>5</b> have unique π-conjugated systems consisting of doubly bridged triphenylene dimer, triphenylene–benzoacenaphthylene, and triphenylene–biphenyl structures, respectively. Quantum mechanical calculations suggested that these π-conjugated systems are aromatic. Containing no metal atom, methylated derivatives <b>3b</b>, <b>4b</b>, and <b>5b</b> exhibited green, pale yellow, and turquoise blue emissions with quantum yields of 0.066, 0.12, and 0.24, respectively. The application of these materials in organic light-emitting diodes was demonstrated

Molecular and Supramolecular Control of the Work Function of an Inorganic Electrode with Self-Assembled Monolayer of Umbrella-Shaped Fullerene Derivatives

The surface properties of inorganic substrates can be altered by coating with organic molecules, which may result in the improvement of the properties suitable for electronic or biological applications. This article reports a systematic experimental study on the influence of the molecular and supramolecular properties of umbrella-shaped penta(organo)[60]fullerene derivatives, and on the work function and the water contact angle of indium–tin oxide (ITO) and gold surfaces. We could relate these macroscopic characteristics to single-molecular level properties, such as ionization potential and molecular dipole. The results led us to conclude that the formation of a SAM of a polar compound generates an electronic field through intermolecular interaction of the molecular charges, and this field makes the overall dipole of the SAM much smaller than the one expected from the simple sum of the dipoles of all molecules in the SAM. This effect, which was called depolarization and previously discussed theoretically, is now quantitatively probed by experiments. The important physical properties in surface science such as work function, ionization potential, and water contact angles have been mutually correlated at the level of molecular structures and molecular orientations on the substrate surface. We also found that the SAMs on ITO and gold operate under the same principle except that the “push-back” effect operates specifically for gold. The study also illustrates the ability of the photoelectron yield spectroscopy technique to rapidly measure the work function of a SAM-covered substrate and the ionization potential value of a molecule on the surface

Efficient Diels–Alder Addition of Cyclopentadiene to Lithium Ion Encapsulated [60]Fullerene

Much higher reactivity of [Li⁺@C₆₀]PF₆^– for Diels–Alder cycloaddition toward cyclopentadiene (CpH), in comparison with that of empty C₆₀, was observed. The synthetic method, electrochemical and light absorption properties, and X-ray crystal structure of the product [Li⁺@C₆₀(CpH)]PF₆^– are discussed

Acceleration of Tri-Addition to [70]Fullerene by “Nanom Black” Fullerene Soot

<div><p>We report the structure and properties of a fullerene soot called “Nanom Black,” which is prepared by removing fullerenes from the soot formed in fullerene production. Nanom Black remarkably accelerates the regioselective tri-addition of phenylcopper reagent to C₇₀, giving C₇₀Ph₃H at a reaction rate approximately 50-fold that in the absence of Nanom Black. Transmission electron microscopy, X-ray diffraction, and Raman data on Nanom Black are presented, and a mechanistic rationale is discussed. </p> </div

Structurally Defined High-LUMO-Level 66π-[70]Fullerene Derivatives: Synthesis and Application in Organic Photovoltaic Cells

Two new reactions for the synthesis of structurally defined 66π-electron [70]­fullerene derivatives are reported. The first provides synthetic access to tetra-phenyl or [3 + 1] hybrid tetra-aryl C₇₀ adducts via oxidation of a fullerene copper complex [Ar₃C₇₀–Cu–Ar′]⁻ (Ar = Ph, 4-ⁿBuC₆H₄; Ar′ = Ph, 4-MeOC₆H₄). The second provides access to alkyl fullerene ethers, C₇₀Ar₃(2-EH) via AgClO₄-mediated coupling of a [70]­fullerene bromide C₇₀Ar₃Br with 2-ethylhexanol (2-EH). The first reaction afforded two types of regioisomers including a 3,10,22,25-adduct (denoted type I) and a 7,10,22,25-adduct (type II). The haptotropic migration of the copper on a cuprio fullerene intermediate was suggested to be responsible for the generation of the two regioisomers. The second reaction gave only one regioisomer (type II). The eight new 66π-electron [70]­fullerene derivatives synthesized are electrochemically and thermally stable, and their photoabsorption and electrochemical properties are closely related to the addition pattern. For example, the type II regioisomers have higher LUMO levels than the type I isomers. Through modification of the addends, the LUMO levels of these [70]­fullerene derivatives can be raised by as much as 220 meV, that is, from −3.80 to −3.58 eV. Solution-processed p-n junction organic photovoltaic devices using five soluble compounds <b>5</b>, <b>9</b>, <b>10</b>, <b>13</b>, and <b>15</b> as the n-type semiconducting materials were fabricated. The device using compound <b>15</b> (LUMO = −3.58 eV) showed the highest open circuit voltage (<i>V</i>_oc = 0.90 V) and a respectable PCE value of 3.33%. For <i>J</i>_sc and FF, type II compounds <b>10</b>, <b>13</b>, and <b>15</b> showed much higher values than did type I compounds <b>5</b> and <b>9</b>, suggesting that the type II addition pattern on C₇₀ may be superior to the type I pattern for efficient electron transport, likely because of better molecular packing in crystals as suggested by crystallographic data

Synthesis and Crystal Structure of Li⁺@Fluoreno[60]fullerene: Effect of Encapsulated Lithium Ion on Electrochemistry of Spiroannelated Fullerene

The reaction of [Li⁺@C₆₀]­TFSI^– (TFSI = bis­(trifluoromethanesulfonyl)­imide) with 9-diazofluorene directly produced a [6,6]-adduct of lithium-ion-containing fluoreno[60]­fullerene, [6,6]-[Li⁺@C₆₀(fluoreno)]­TFSI^–, which was crystallographically characterized. Cyclic voltammetry of the compound showed a reversible one-electron reduction wave at −0.51 V (vs Fc/Fc⁺) and an irreversible reduction wave for the second electron. The latter was attributed to opening of the three-membered ring due to strong stabilization of the resulting sp³-carbanion by the encapsulated Li⁺ and formation of a 14π-electron aromatic fluorenyl anion