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Azo compounds are efficient electron acceptors. Upon one-electron reduction they generally isomerize forming the thermodynamically most stable radical anion. Herein we show that the size of the central ring in 1,2-diazocines and diazonines has a ruling influence on the configuration of the one-electron reduced species. Markedly, diazonines, which bear a central nine membered heterocycle, show light-induced E/Z isomerization, but retain the configuration of the diazene N=N moiety upon one-electron reduction. Accordingly, E/Z isomerization is not induced by reduction.
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http://dx.doi.org/10.1002/chem.202300146 | DOI Listing |
Phys Chem Chem Phys
September 2025
Faculty of Chemistry, Northeast Normal University, Changchun 130024, China.
The photocatalytic performance of d-block metal complexes with unsaturated coordination circumstances after one dative-bond cleavage has become an emerging domain. Especially, the photocatalytic CO reduction reaction (CORR) on the active center of d-block metals in tridentate/bidentate ligands with square pyramidal nitrogen-coordinated atoms has been reported. In this study, the photocatalytic CORR performance of six metals in [TM(tpy)(ppy)] as possible active candidates (TM = Fe, Co, Ru, Rh, Re, and Ir) for CO production was evaluated in detail using DFT computations.
View Article and Find Full Text PDFChemistry
September 2025
Department of Chemistry, Graduate School of Science, Tohoku University, Aoba-ku, Sendai, 9808578, Japan.
Phosphorus(V)-centered porphyrins (P(V)-porphyrins) are an important class of functional dyes in many fields of research, and axial ligands on the phosphorus atom affect the electronic properties of P(V)-porphyrins and add functions. Herein, we report on the synthesis and characterization of a hitherto unknown P(V)-porphyrin having hydrogen atoms as axial ligands (1·PF , PF is a counter anion). Synthesis of 1·PF was achieved by treatment of dichloro-derivative (2·Cl) with LiAlH followed by AgPF via hydride reduction accompanied by one-electron reduction and one-electron oxidation.
View Article and Find Full Text PDFEnviron Sci Technol
September 2025
State Key Laboratory of Pollution Control and Resources Reuse, Tongji University, Shanghai 200092, China.
Ferrous iron (Fe(II)) species are prevalent in reductive subsurface environments, where some active Fe(II) species can generate hydroxyl radical (·OH) during oxidation under O perturbation, facilitating pollutant attenuation. However, aqueous Fe(II), a common form of ferrous iron, can be rapidly oxidized but scarcely contributes to ·OH production. Herein, this study proposes a thermodynamic control strategy by introducing micro-nanobubbles (MNBs) into an aqueous Fe(II)/O system to stimulate its potential.
View Article and Find Full Text PDFInorg Chem
September 2025
Department of Chemistry and Biochemistry, Institute for Inorganic and Materials Chemistry, Faculty of Mathematics and Natural Sciences, University of Cologne, Greinstrasse 6, 50939 Koeln, Germany.
Two Ni(II) complexes, -[Ni(CF)(IPy)] () and -[Ni(CF)(PyImMe)] (), containing the N^C coordinating pyridyl--heterocyclic carbene (NHC) ligands, IPy = 1,3-di(pyridin-2-yl)-imidazole-2-ylidene and PyImMe = 1-(pyridin-2-yl)-3-methyl-imidazole-2-ylidene, were synthesized and analyzed through elemental analysis, H and F NMR, and HR-ESI-MS(+) mass spectrometry. The diamagnetic complexes show square planar configurations around Ni(II) as shown by single-crystal X-ray diffraction. The geometries were used to benchmark density functional theory (DFT) calculated geometries, which were used for single point and time-dependent DFT (TD-DFT) calculations using the TPSSh functional.
View Article and Find Full Text PDFJ Biol Chem
August 2025
Department of Biochemistry, University of California, Riverside.
We have investigated the rapid-reaction kinetics of the NAD-dependent NADPH:ferredoxin oxidoreductase II (NfnII) from Pyrococcus furiosus, permitting a comparison with recent work done with the paralog NfnI from the same organism. The half-potentials of the electron-bifurcating L-FAD are highly crossed in both NfnI, meaning the potential for the quinone/semiquinone couple is significantly lower than that for the semiquinone/hydroquinone couple so that the semiquinone oxidation state is thermodynamically unstable. The same appears to be the case with NfnII on the basis of its similar behavior in transient absorption spectroscopy experiments and the absence of any evidence for FAD• accumulation in the course of reductive titrations (which would be manifested as a transient increase in absorbance at ∼380 nm).
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