J. Appl. Cryst.の発刊に際して

Advancing perovskite solar cell technologies toward their theoretical power conversion efficiency (PCE) requires delicate control over the carrier dynamics throughout the entire device. By controlling the formation of the perovskite layer and careful choices of other materials, we suppressed carrier recombination in the absorber, facilitated carrier injection into the carrier transport layers, and maintained good carrier extraction at the electrodes. When measured via reverse bias scan, cell PCE is typically boosted to 16.6% on average, with the highest efficiency of ~19.3% in a planar geometry without antireflective coating. The fabrication of our perovskite solar cells was conducted in air and from solution at low temperatures, which should simplify manufacturing of large-area perovskite devices that are inexpensive and perform at high levels.

http://science.sciencemag.org/content/sci/345/6196/542.full.pdf

Interface engineering of highly efficient perovskite solar cells

Electrogenerated chemiluminescence (also called electrochemiluminescence and abbreviated ECL) is the process whereby species generated at electrodes undergo high-energy electron-transfer reactions to form excited states that emit light. The first detailed ECL studies were described by Hercules and Bard et al. in the mid-1960s, although reports concerning light emission during electrolysis date back to the 1920s by Harvey. After about 40 years study, ECL has now become a very powerful analytical technique and been widely used in the areas of, for example, immunoassay, food and water testing, and biowarfare agent detection. ECL has also been successfully exploited as a detector of flow injection analysis (FIA), high-performance liquid chromatography (HPLC), capillary electrophoresis, and micro total analysis (μTAS). Figure 1 illustrates a time line of various events in the development of ECL. A literature survey using SciFinder Scholar reveals that more than 2000 journal articles, book chapters, and patents on various topics of ECL have been published. The overall number of publications, as shown in Figure 2, has increased exponentially over the past 20 years, of which 40–50% were biorelated. Similar amounts of ECL papers could be also found from the Thomson ISI Web of Science as well as † Telephone (601) 266 4716; fax (601) 266 6075; e-mail wujian.miao@ usm.edu. Wujian Miao received his undergraduate diploma in chemistry from Nantong University (Nantong, China) in 1982, his M.Sc. degree in analytical chemistry from Zhongshan University (Guangzhou, China, with Jinyuan Mo) in 1991, and his Ph.D. degree in electrochemistry from Monash University (Melbourne, Australia, with Alan M. Bond) in 2000. He then served as a Research Scientist in CSIRO (Melbourne, Australia), followed by a postdoctoral fellowship at the University of Texas at Austin with Allen J. Bard in 2001. Since 2004 he has served as an assistant professor of chemistry at the University of Southern Mississippi.

Electrogenerated Chemiluminescence and Its Biorelated Applications

https://www.pnas.org/content/pnas/90/5/1635.full.pdf

Supramolecular chemistry.

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The reaction between 9-carboxy-10-methylacridinium phenyl ester (CMAPE) and hydrogen peroxide leading to the formation of electronically excited 10-methyl-9-acridinone has been examined at the semiempirical PM3 level of theory. The reaction mechanisms proposed in the literature were verified and the details of the rather complicated processes leading to the emission of light (chemiluminescence) explained by these theoretical studies. Particular reaction steps were characterized at the thermodynamic and kinetic levels. The influence of the solvent was studied by means of the PM3-COSMO method (aqueous medium). The bottleneck steps determining the kinetics of the overall process were identified. Structural modifications of CMAPE that could improve its analytical usefulness were indicated on the basis of theoretical considerations.

Toward an Understanding of the Chemiluminescence Accompanying the Reaction of 9-Carboxy-10-methylacridinium Phenyl Ester with Hydrogen Peroxide.

Properties of multiply-charged hexafluorometallates MF{sub 6}{sup 3-}, M = Sc, Y, La, ZrF{sub 6}{sup 2-}, and TaF{sub 6}{sup -}, have been examined at the SCF, MP2 and Becke3LYP levels of theory using the SBKJ pseudopotentials and extended one-electron basis sets. For MF{sub 6}{sup 3-}, M = Sc, Y, La, our results suggest a different assignment of vibrational transitions than those quoted by Nakamoto and recorded by von Becker et al. For the series of isoelectronic complexes, we document that the discrepancy between the theoretical gas phase vibrational frequencies and those measured in condensed phase experiments increases as the Becke3LYP HOMO binding energies become more positive. The frequencies of stretching modes measured in condensed phase experiments are systematically higher than those calculated for the gas phase anions. We suggest that a partial charge transfer from the multiply-charged anions to countercations is responsible for the stiffening of vibrational modes in condensed phase environments. The vertical electron detachment energies were determined at the outer valence Green`s function, MP2, and B3LYP levels. The binding energies of hexafluorometallates with respect to the energies of atomic ions were also calculated and only a small contribution of the electron correlation effects was found. 85 refs., 6 figs.

Properties of Closed-Shell, Octahedral, Multiply-Charged Hexafluorometallates MF63-, M = Sc, Y, La, ZrF62-, and TaF6-

The thermal decomposition of quaternary methylammonium halides was studied using thermogravimetry coupled to FTIR (TG-FTIR) and differential scanning calorimetry (DSC) as well as the DFT, MP2 and G2 quantum chemical methods. There is almost perfect agreement between the experimental IR spectra and those predicted at the B3LYP/6-311G(d,p) level: this has demonstrated for the first time that an equimolar mixture of trimethylamine and a methyl halide is produced as a result of decomposition. The experimental enthalpies of dissociation are 153.4, 171.2, and 186.7 kJ/mol for chloride, bromide and iodide, respectively, values that correlate well with the calculated enthalpies of dissociation based on crystal lattice energies and quantum chemical thermodynamic barriers. The experimental activation barriers estimated from the least-squares fit of the F1 kinetic model (first-order process) to thermogravimetric traces – 283, 244 and 204 kJ/mol for chloride, bromide and iodide, respectively – agree very well with theoretically calculated values. The theoretical approach assumed in this work has been shown capable of predicting the relevant characteristics of the thermal decomposition of solids with experimental accuracy.

TG-FTIR, DSC and quantum chemical studies of the thermal decomposition of quaternary methylammonium halides

10-Methyl-9-(phenoxycarbonyl)acridinium trifluoromethanesulfonates bearing alkyl substituents at the benzene ring were synthesized, purified, and identified. In the reaction with OOH− in basic aqueous media, the cations of the compounds investigated were converted to electronically excited 10-methyl-9-acridinone, whose relaxation was accompanied by chemiluminescence (CL). The kinetic constants of CL decay, relative efficiencies of light emission, chemiluminescence quantum yields, and resistance toward alkaline hydrolysis were determined experimentally under various conditions. The mechanism of CL generation is considered on the basis of thermodynamic and kinetic parameters of the reaction steps predicted at the DFT level of theory. The chemiluminescence efficiency is the result of competition of the electrophilic center at C(9) between nucleophilic substitution by OOH− or OH− and the ability of the intermediates thus formed to decompose to electronically excited 10-methyl-9-acridinone. Identification of s...

Chemiluminogenic features of 10-methyl-9-(phenoxycarbonyl)acridinium trifluoromethanesulfonates alkyl substituted at the benzene ring in aqueous media.

Jerzy Błażejowski

Papers

Toward an Understanding of the Chemiluminescence Accompanying the Reaction of 9-Carboxy-10-methylacridinium Phenyl Ester with Hydrogen Peroxide.

Properties of Closed-Shell, Octahedral, Multiply-Charged Hexafluorometallates MF63-, M = Sc, Y, La, ZrF62-, and TaF6-

TG-FTIR, DSC and quantum chemical studies of the thermal decomposition of quaternary methylammonium halides

Chemiluminogenic features of 10-methyl-9-(phenoxycarbonyl)acridinium trifluoromethanesulfonates alkyl substituted at the benzene ring in aqueous media.

Thermal properties of amine hydrochlorides: Part II. Thermolysis and thermochemistry of alkanaminium chlorides