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

Synthesis and Properties of Bingel-type Methanofullerene−π-Extended-TTF Diads and Triads

Novel C60/π-extended tetrathiafulvalene (exTTF) diads (12a−c) and triads [D2A (14a−c) and DA2 (25, 27a−c)] have been synthesized by the Bingel cyclopropanation reaction of the respective exTTF-containing malonates and [60]fullerene. The reaction of exTTF-bismalonates with C60 affords the respective C60−exTTF diads (26a−c) together with the triad C60−exTTF−C60 (25, 27a−c) and a regioisomeric mixture of bisadducts (28b−c). Theoretical calculations (PM3) predict the favored geometry for triads 14a−c depending upon the orientation (up and down) of the 1,3-dithiole rings in the exTTFs, as well as the more stable regioisomers for the bisadducts 28. Cyclic voltammetry measurements reveal that C60 and exTTF units do not intereact in the ground state. Compounds 26a−c and 27a−c are not electrochemically stable. A photoinduced electron transfer leading to the formation of the radical pair (C60-−exTTF•+) has been observed for compounds 14a−c

Synthesis and Photophysical Investigation of New Porphyrin Derivatives with β-Pyrrole Ethynyl Linkage and Corresponding Dyad with [60] Fullerene

Two new β-substituted arylethynyl meso-tetraphenylporphyrins, 2-[(4‘-formyl)phenyl]ethynyl-5,10,15,20-tetraphenylporphyrin (system A) and 2-[(4‘-methyl)phenyl]ethynyl-5,10,15,20-tetraphenylporphyrin (system B) and their zinc derivatives were synthesized by palladium catalysis, using a synthetic approach that affords high yields of the target systems. Comparative ultraviolet−visible (UV−vis), NMR, and cyclic voltammetry studies of such macrocycles reveal the presence of an extensive conjugation between the tetrapyrrolic ring and the linker, through π−π orbital interaction. This interaction was observed in the form of a “push−pull” effect that moves the electronic charge between the porphyrin and the aldehyde group of system A. System B, bearing a methyl group instead of the formyl group, was synthesized in order to evaluate the effect of the substitution on the charge delocalization, which is necessary to corroborate the push−pull mechanism hypothesis. The new porphyrin, system A, was also used as a starting material for the synthesis of new porphyrin−fullerene dyads in which the [60]fullerene is directly linked to the tetrapyrrolic rings by ethynylenephenylene subunits. Fluorescence and transient absorption measurements of the new dyads reveal that ultrafast energy and electron transfer occur, respectively, in nonpolar and polar solvents, with high values of the rate constant. The UV−vis, NMR, and cyclic voltammetry results show that it is possible for both energy and electron transfer between porphyrin and fullerene to take place through the π-bond interaction. Such results evidence that the coupling between the donor and acceptor moieties is strong enough for possible photovoltaic applications

Zero- versus One-Dimensional Water-Soluble CdTe NanocrystalsSynthesis and Photophysical Characterization

This work demonstrates the systematic development and characterization of water-soluble one-dimensional nanorods of CdTe (QR) with the assistance of a mixed ligand system, namely, a combination of 2-(dimethylamino)ethanethiol and cysteine, that both serve as surface stabilizers. Their characterization has been accomplished by means of a wide range of microscopic and photophysical techniques. The corresponding three-dimensional quantum dots of CdTe (QD) emerged as important reference systems, especially for the different photophysical assays. The latter were exclusively formed when just 2-(dimethylamino)ethanethiol was used as surface stabilizer. A maximum photoluminescence quantum yield of 25% was estimated for QR samples that were refluxed in water for approximately 11 h. Such remarkably high quantum yields, which are appreciably higher than what is seen for the analogous QD, point to a successful control over defects, trapping states, etc. In line with this trend is the observation that the excited-state lifetime of the QR is longer than in analogous QD

Pairing Fullerenes and Porphyrins: Supramolecular Wires That Exhibit Charge Transfer Activity

A concept is elaborated of pairing electron donors and electron acceptors that share a common trait, wire-like features, as a powerful means to realize a new and versatile class of electron donor−acceptor nanohybrids. Important variables are fine-tuning (i) the complexation strength, (ii) the electron/energy transfer behavior, and (iii) the solubilities of the resulting architectures. In particular, a series of supramolecular porphyrin/fullerene hybrids assembled by the hydrogen bonding of Hamilton receptor/cyanuric acid motif has been realized. Putting the aforementioned variables into action, the association constants (Kass), as they were determined from 1H NMR and steady-state fluorescence assays, were successfully tweaked with values in the range of 104−105 M−1. In fact, our detailed studies corroborate that the latter reveal a dependence on the nature of the spacer, that is, p-phenylene-ethynylene, p-phenylene-vinylene, p-ethynylene, and fluorene, as well as on the length of the spacer. Complementary performed transient absorption studies confirm that electron transfer is indeed the modus operandi in our novel class of electron donor−acceptor nanohybrids, while energy transfer plays, if any, only a minor role. The accordingly formed electron transfer products, that is, one-electron oxidized porphyrins and one-electron reduced fullerenes, are long-lived with lifetimes that reach well into the time domain of tens of nanoseconds. Finally, we have used the distance dependence on electron transfer, charge separation and charge recombination, to determine for the first time a β value (0.11 Å−1) for hydrogen-bonding-mediated electron transfer

Highly Coupled Dyads Based on Phthalocyanine−Ruthenium(II) Tris(bipyridine) Complexes. Synthesis and Photoinduced Processes

A new series of multicomponent ZnPc−Ru(bpy)3 systems, 1a−c, consisting of a zinc-phthalocyanine linked through conjugated and/or nonconjugated connections to a ruthenium(II) tris(bipyridine) complex, has been synthesized. The ruthenium complexes 1a−c were prepared from phthalocyanines 2a−c, bearing a 4-substituted-2,2‘-bipyridine ligand by treatment with [Ru(bpy)2Cl2]·2H2O. Different synthetic strategies have been devised to prepare the corresponding dyad precursors (2a−c). Compound 2a, for example, with an ethenyl bridge, was synthesized by statistical condensation of 4-tert-butylphthalonitrile and 5-[(E)-2-(3,4-dicyanophenyl)ethenyl]-2,2‘-bipyridine (3) in the presence of zinc chloride. Compounds 2b and 2c, having, respectively, an amide or an ethynyl bridge, were prepared following a different synthetic approach. The method involves the coupling of an appropriate 5-substituted-2,2‘-bipyridine to an unsymmetrical phthalocyanine suitably functionalized with an amino (4) or an ethynyl group (5). The photophysical properties of the dyads that are ZnPc−Ru(bpy)3 1a−c and related model compounds have been determined by a variety of steady-state (i.e., fluorescence) and time-resolved methods (i.e., fluorescence and transient absorption). Clearly, intramolecular electronic interactions between the two subunits dominate the photophysical events following the initial excitation of either chromophore. These intramolecular interactions lead, in the case of photoexcited ZnPc, to faster intersystem crossing kinetics compared to a ZnPc reference, while photoexcited [Ru(bpy)3]2+ undergoes a rapid and efficient transduction of triplet excited-state energy to the Pc

Addition Reaction of Azido-exTTFs to C₆₀: Synthesis of Fullerotriazoline and Azafulleroid Electroactive Dyads

The addition reaction of azido-exTTFs to C60 affords electroactive fullerotriazoline and azafulleroid dyads, which behave as amphoteric redox systems. Fluorescence experiments and transient absorption spectroscopy reveal that excitation of the fullerene moiety leads to radical pair lifetimes that are 2 orders of magnitude higher than those previously reported for related fullerotriazolines

Novel Porphyrin-Fullerene Assemblies: from Rotaxanes to Catenanes

Titration of porphyrin-fullerene rotaxanes with DABCO or 4,4‘-bipyridine led to photo- and redoxactive catenanic architectures, which upon photoexcitation undergo a sequence of short-range energy and electron transfer events to give a long-lived charge-separated radical-pair state

Improved Carrier Collection and Hot Electron Extraction Across Perovskite, C₆₀, and TiO₂ Interfaces

The use of C60 as an interfacial layer between TiO2 and methylammonium lead iodide perovskite is probed to reduce the current–voltage hysteresis in perovskite solar cells (PSCs) and, in turn, to impact the interfacial carrier injection and recombination processes that limit solar cell efficiencies. Detailed kinetic analyses across different time scales, that is, from the femtoseconds to the seconds, reveal that the charge carrier lifetimes as well as the charge injection and charge recombination dynamics depend largely on the presence or absence of C60. In addition, we corroborate that C60 is applicable in hot carrier PSCs as it is capable of extracting hot carriers generated throughout the early time scales following photoexcitation

Drastic Changes in the Lifetime and Electron Transfer and Energy Transfer Reactivity of the Triplet Excited State of <i>p</i>-Benzoquinone by Complex Formation with Scandium Ion Salts

Metal-ion salts such as scandium triflate form strong complexes with the triplet excited state of p-benzoquinone, which have extremely long lifetimes as compared with the lifetime of the uncomplexed quinone triplet, whereas no complex is formed with metal-ion salts in the ground state. The absorption maxima (λmax) of triplet−triplet absorption of the metal-ion salt complexes are red-shifted from the λmax value of the uncomplexed quinone triplet and vary depending on the Lewis acidity of the metal-ion salts. The rate of the complexation of the triplet excited state with scandium triflate is determined, obeying pseudo-first-order kinetics. The pseudo-first-order rate constant increases linearly with increasing metal-ion concentration. The transient absorption spectra of donor radical cations produced by photoinduced electron transfer from N,N-dimethylanilines to the triplet excited state of p-benzoquinone are detected by laser-flash photolysis measurements, whereas no such radical cations are detected in the presence of scandium triflate under otherwise the same experimental conditions. Thus, the electron transfer reactivity of the triplet excited state complex of p-benzoquinone with scandium triflate toward electron donors is diminished significantly as compared with that of the uncomplexed quinone triplet. In contrast, the energy transfer from the triplet excited state to oxygen is enhanced by complex formation with scandium triflate