J. Appl. Cryst.の発刊に際して

1. Advantages of Chemical Redox Agents 878 2. Disadvantages of Chemical Redox Agents 879 C. Potentials in Nonaqueous Solvents 879 D. Reversible vs Irreversible ET Reagents 879 E. Categorization of Reagent Strength 881 II. Oxidants 881 A. Inorganic 881 1. Metal and Metal Complex Oxidants 881 2. Main Group Oxidants 887 B. Organic 891 1. Radical Cations 891 2. Carbocations 893 3. Cyanocarbons and Related Electron-Rich Compounds 894

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Chemical Redox Agents for Organometallic Chemistry

: The unpolarized absorption and circular dichroism spectra of the fundamental vibrational transitions of the chiral molecule, 4-methyl-2-oxetanone, are calculated ab initio. Harmonic force fields are obtained using Density Functional Theory (DFT), MP2, and SCF methodologies and a 5S4P2D/3S2P (TZ2P) basis set. DFT calculations use the Local Spin Density Approximation (LSDA), BLYP, and Becke3LYP (B3LYP) density functionals. Mid-IR spectra predicted using LSDA, BLYP, and B3LYP force fields are of significantly different quality, the B3LYP force field yielding spectra in clearly superior, and overall excellent, agreement with experiment. The MP2 force field yields spectra in slightly worse agreement with experiment than the B3LYP force field. The SCF force field yields spectra in poor agreement with experiment.The basis set dependence of B3LYP force fields is also explored: the 6-31G* and TZ2P basis sets give very similar results while the 3-21G basis set yields spectra in substantially worse agreements with experiment. jg

Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields

The development of microgels/nanogels for drug delivery applications

Advances in copper complexes as anticancer agents.

Herein, we report a mild and efficient palladium-catalyzed C–H functionalization method to synthesize a series of benzoquinone (BQ)-based charge-transfer (CT) derivatives in good yields. The optoelectronic properties of these compounds were explored both theoretically and experimentally and correlations to their structures were identified as a function of the nature and position of the donor group (meta and para) attached to the benzoquinone acceptor. Compound 3, where benzoquinone is para-conjugated to the diphenylamine donor group, exhibited thermally activated delayed fluorescence (TADF) with a biexponential lifetime characterized by a prompt ns component and a delayed component of 353 μs.

https://www.beilstein-journals.org/bjoc/content/pdf/1860-5397-15-285.pdf

Synthesis and optoelectronic properties of benzoquinone-based donor-acceptor compounds.

Synthesis of α-Heterosubstituted Glycine Derivatives from Dihaloethanamides.

The reaction of trans-[Mn(CN)(CO)(dppm)2] with [Fe{P(OMe)3}(NO)2(η-C3H4R)][PF6](R z. H, 1-Me, or 2-Me) in tetrahydrofuran (thf) results in allylic alkylation of the cyanide ligand to give the allyl isocyanide complexes trans-[Mn(CO)(CNCH2CMeCH2)(dppm)2][PF6]·thf and trans-[Mn(CO)(CNCH2CHCHR)(dppm)2][PF6]·thf (RH or Me). The X-ray crystal structure of trans-[Mn(CO)(CNCH2CMeCH2)(dppm)2][PF6]·thf shows that in the cation the manganese(I) atom has approximately octahedral co-ordination, with the carbonyl and 2-methylallyl isocyanide ligands mutually trans, and the chelating dppm ligands occupying the four equatorial sites.

Allylic alkylation of co-ordinated cyanide: the synthesis and X-ray crystal structure of trans-[Mn(CO)(CNCH2CMe:CH2)*dppm)2][PF6].thf

Regioselective stepwise phenylation of 4,7-diarylbenzo[c][1,2,5]thiadiazole fluorophores has been achieved through a facile one-pot, three-step synthetic strategy involving sequential borylation, hydroxydechlorination and Suzuki–Miyaura cross-coupling reactions. Crucial to the selectivity was the use of BCl3 to regioselectively install a boronic acid group in the ortho-position of only one of the diaryl groups. The subsequent introduction of ortho-phenyl groups through Suzuki–Miyaura cross-coupling gave rise to twisted structures with hindered intramolecular rotation, providing a structural lever with which the fluorophore absorption and emission properties could be adjusted.

Georgina M. Rosair

Papers

Synthesis and optoelectronic properties of benzoquinone-based donor-acceptor compounds.

Synthesis of α-Heterosubstituted Glycine Derivatives from Dihaloethanamides.

Allylic alkylation of co-ordinated cyanide: the synthesis and X-ray crystal structure of trans-[Mn(CO)(CNCH2CMe:CH2)*dppm)2][PF6].thf

Regioselective electrophilic aromatic borylation as a method for synthesising sterically hindered benzothiadiazole fluorophores

Supraicosahedral (Metalla) Carboranes