Article
Chemistry, Physical
Qing Chen, Zhaoxian Qin, Shuang Liu, Mingchang Zhu, Gao Li
Summary: This study presents a novel method to convert the anionic [Ag16Au13L24](3-) nanocluster into a charge neutral nanocluster of [Ag16Au13L24](0) via oxidation using H2O2 as the oxidant. The three-electron loss process during oxidation was confirmed by electron paramagnetic resonance and mass spectrometry. The one-way conversion process is monitored in situ by UV-visible spectroscopy, showing a nanocluster charge effect manifested in the spectra.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Multidisciplinary
Bin Li, Blaise L. Geoghegan, Christoph Woelper, George E. Cutsail, Stephan Schulz
Summary: This study systematically investigates the reactivity of beta-diketiminate zinc complexes with the redox-active 2,2'-bipyridine. The results show that bpy can serve as a neutral ligand, a p-radical anion, or a diamagnetic dianion in different reactions with LZnI, NaB(C6F5)(4), and KC8. The electronic structure of the complexes is elucidated through various experimental and theoretical methods, revealing the collaborative role of the beta-diketiminate co-ligand and bpy ligand in stabilizing the energy of the LUMO.
Article
Chemistry, Multidisciplinary
Ute Wild, Olaf Huebner, Paul Meiners, Elisabeth Kaifer, Markus Enders, Hans-Joerg Himmel
Summary: By using unconventional synthesis protocols, researchers have successfully connected two redox-active triguanidine units through a dithiolate bridge. They achieved intramolecular through-space double-electron transfer between the two units at low temperatures, and observed chemical exchange between different redox states. These findings provide detailed quantitative insights into the factors influencing intramolecular through-space double-electron transfer processes.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Tomoya Imai, Daisuke Sakamaki, Shinobu Aoyagi, Toru Amaya
Summary: The design and synthesis of a cyclic [3]spirobifluorenylene molecule with bulky alkyl groups allows for investigation into electron transfer phenomena in a pi-conjugated system. The molecule exhibits intramolecular electron transfer and spin delocalization, making it a useful tool for studying electron transfer in molecular wires.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Environmental Sciences
Lin Chen, Tingting Fan, Min Yang, Dunfeng Si, Haotian Wu, Song Wu, Jian Xu, Dongmei Zhou
Summary: The study investigates the changes in physicochemical and redox properties of microplastics under a reducing environment and their interaction with arsenite. The results show that sulfurized microplastics have lower efficiency in mediating arsenite oxidation due to decreased electron donating capacity.
SCIENCE OF THE TOTAL ENVIRONMENT
(2023)
Article
Chemistry, Multidisciplinary
Chun-Hong Hu, Yueqian Sang, Ya-Wei Yang, Wen-Wen Li, Hui-Lin Wang, ZiYing Zhang, Chen Ye, Li-Zhu Wu, Xiao-Song Xue, Yang Li
Summary: The article presents a solution to the challenge of direct decarboxylation, by utilizing a charge-transfer complex of aryl carboxylate that induces chemoselective decarboxylation to aryl radicals. This method offers potential for mild and versatile arylations in various fields.
Article
Chemistry, Multidisciplinary
Marco Werr, Elisabeth Kaifer, Markus Enders, Andika Asyuda, Michael Zharnikov, Hans-Joerg Himmel
Summary: By subjecting two homoleptic copper(II) complexes to one-electron oxidation, monocationic copper(I) complexes with two oxidised ligands can be obtained. These complexes exhibit different properties in the solid state, possess multiple redox states, and demonstrate strong stability, making them attractive for various applications.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Oksana Azpitarte, Ane Zudaire, Jon Uranga, Xabier Lopez, Luca Salassa, Elena Formoso, Elixabete Rezabal
Summary: The unconventional bioorthogonal catalytic activation of anticancer metal complexes by flavin and flavoproteins photocatalysis has been recently reported. The reactivity is based on a two-electron redox reaction of the photoactivated flavin. In addition, site mutagenesis has been found to modulate and improve the catalytic activity of mini Singlet Oxygen Generator protein (SOG). The redox properties of flavin and the resulting reactivity of miniSOG are modulated by specific mutations, which is consistent with experimental results.
Article
Engineering, Chemical
Yuan Gao, Yi Tan, Wenliang Qi, Zhiqiang Hu, Pengting Li
Summary: Removing stubborn B from Si efficiently and simplifying the purification process are critical challenges in the manufacture of solar grade silicon via metallurgical routes. This study presents a method to address these challenges by flexibly coupling B with other impurities separation procedure, and purifying metallurgical grade silicon through simplified electron beam melting unlocked by a few oxides. The method not only ensures the smooth process of B oxidation, but also favors the co-removal of other impurities, achieving high purity Si.
SEPARATION AND PURIFICATION TECHNOLOGY
(2023)
Article
Engineering, Environmental
Liping Fang, Zebin Hong, Thomas Borch, Qiantao Shi, Fangbai Li
Summary: This study found that under anoxic conditions, iron oxyhydroxides (such as goethite) can facilitate the oxidation of As(III) while reducing structural Fe(III). The formation of an active metastable Fe(III) phase at the defective surface of goethite, through atom exchange, is responsible for the oxidation of As(III). Defects in goethite significantly enhance electron transfer and atom exchange between surface-bound Fe(II) and structural Fe(III), resulting in an increase in As(III) oxidation. Atom exchange-induced regeneration of active goethite sites facilitates As(III) coordination and electron transfer with Fe(III). These findings shed new light on As risk management in soils and subsurface environments by highlighting the synergetic effects of defects in the Fe crystal structure and Fe(II)-induced catalytic processes on anoxic As(III) oxidation.
ENVIRONMENTAL SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Physical
Jesus Lucia-Tamudo, Sergio Diaz-Tendero, Juan J. Nogueira
Summary: The use of DNA strands as nanowires or electrochemical biosensors requires understanding of charge transfer processes and redox properties. This study computationally assesses these properties, determining ionization energies, attachment energies, oxidation potentials, and delocalization of the hole for nucleobases in free form and as part of DNA strands. The reducer ability of nucleobases is explained by intramolecular delocalization of the charged hole, while the enhancement of reducer character in the strand correlates well with intermolecular hole delocalization. DNA strand redox properties can be tuned by balancing intramolecular and intermolecular charge delocalization.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Organic
Sanjay Yadav, Jagadeesh Babu Nanubolu, Surisetti Suresh
Summary: This Letter presents a simple and effective method for accessing a variety of phenanthro[9,10-b]furan and 1H-dibenzo[e,g]indole derivatives. The method involves a carbenecatalyzed intramolecular Stetter reaction followed by a Paal-Knorr reaction, and has been demonstrated to be applicable on a gram scale and for postsynthetic transformations.
Article
Chemistry, Physical
Angel H. H. Romero, Ivan E. E. Romero, Lourdes Gotopo, Gustavo Cabrera, Hugo Cerecetto
Summary: This study demonstrates that the N-1-(4-chlorophenyl)-2-(trifluoromethyl)benzo[b][1,8]naphthyridin-4(1H)-one fluorophore serves as a convenient platform to selectively promote diverse PCET mechanisms upon phenol binding. The findings provide a new perspective for the rational design of selective and effective photobasic organic modulators of PCET mechanisms.
MOLECULAR SYSTEMS DESIGN & ENGINEERING
(2023)
Article
Chemistry, Multidisciplinary
Sebastian Haaf, Elisabeth Kaifer, Hubert Wadepohl, Hans-Joerg Himmel
Summary: In this study, the manipulation of the electronic structure of copper complexes with a redox-active guanidine ligand was achieved through the use of secondary coordination sphere motifs. The crown ether functions attached to the ligand allowed for control of the degree of intramolecular electron transfer between the guanidine ligand and the copper atom through metal encapsulation.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Zhaoling Zhang, Gaozhang Gou, Jun Wan, Hui Li, Man Wang, Liangchun Li
Summary: A series of asymmetrical silafluorene derivatives were designed and synthesized via a CA-RE reaction, and it was found that their photophysical properties and energy levels could be modulated by varying the peripheral donor units. Some of the derivatives showed significant decreases in energy gaps and unique crystal structures with potential porosity. This research broadens the selection of molecular systems for potential applications in organic optoelectronic devices.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Tomas Chlupaty, Kristyna Brichova, Maksim A. Samsonov, Zdenka Ruzickova, Ales Ruzicka
Summary: In this study, a series of heteroleptic amidotin(II) amidinates and tin(II) bis(benzamidinate) compounds were synthesized, and the reversibility of some reactions was demonstrated through NMR study and DFT description.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Multidisciplinary
Jian Xu, Sudip Pan, Shenglai Yao, Gernot Frenking, Matthias Driess
Summary: The stable plumbylone {[Si-II(Xant)Si-II]Pb-0} 3 and its isolable carbonyl iron complex {[Si-II(Xant)Si-II](PbFe)-Fe-0(CO)(4)} 4 were obtained by reduction reactions. While compound 4 showed relatively good stability, it decomposed to elemental Pb and {[Si-II(Xant)Si-II]Fe(CO)(3)} 5 at higher temperatures. Reaction of 4 with [Rh(CO)(2)Cl](2) yielded the unusual dimeric [(OC)(2)RhPb(Cl)Fe(CO)(4)] complex 6 with Rh-Pb-Fe bonds. The molecular and electronic structures of 3 and 4 were determined by Density Functional Theory (DFT) calculations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Yun Xiong, Shicheng Dong, Shenglai Yao, Chenshu Dai, Jun Zhu, Sebastian Kemper, Matthias Driess
Summary: White phosphorus (P-4) undergoes degradation to produce 2,5-disila-3,4-diphosphapyrrole 2 and two novel functionalized Si=P doubly bonded compounds 3 and 4 when exposed to the new N,N-bis(silylenyl)aniline PhNSi2 1. The transformation of compound 2 into compounds 3 and 4 can be achieved depending on the molar ratio of 1 and P-4 as well as the reaction conditions. These compounds can interconvert through reactions with 1 and P-4.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Multidisciplinary
Shenglai Yao, Artetuis Saddington, Yun Xiong, Matthias Driess
Summary: In this study, a series of compounds containing low-valent central atoms were successfully synthesized using bis(NHSi) ligands with electronically and spatially different spacers. The chemical reactions and electronic structures of these compounds were investigated. By controlling the Si–Si distance, a variety of low-valent compounds of Si, Ge, and Sn elements were synthesized, and the o-carborane-based bis(NHSi) ligand enabled the oxidation of Si and Ge as well as the isolation of new compounds. Furthermore, future research directions were proposed, such as applying bis(NHSi) ligands to other main-group elements and developing acyclic silylene ligands.
ACCOUNTS OF CHEMICAL RESEARCH
(2023)
Article
Chemistry, Inorganic & Nuclear
Dominik Vitek, Ales Ruzicka, Libor Dostal, Roman Jambor
Summary: The effect of chelating ligands and Ge->B interaction on the strength of the Ge OtBu bond was studied, which resulted in the isolation of Ge(II) carbamate. Alcoholysis exchange reactions between substituted phenols and compounds 1 and 2 were studied to synthesize functionalized Ge(II) alkoxides. Phosphane-decorated Ge(II) alkoxides were tested as ligands in reactions with (COD)W(CO)(4) and BH3, leading to the isolation of new complexes.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Lukas Reith, Jan Niklas Hausmann, Stefan Mebs, Indranil Mondal, Holger Dau, Matthias Driess, Prashanth W. W. Menezes
Summary: The redox behavior and active structure of cobalt-iron oxyhydroxides catalysts for the oxygen evolution reaction (OER) are investigated. Quasi in situ X-ray absorption spectroscopy is used to track the redox behavior and identify the active structure, and it is found that iron exhibits substantial redox behavior with an average oxidation state between 2.8 and above 3.2. The contraction of the Fe-O bond length and distortion of the [MO6] octahedra during OER suggest the presence of oxyl radicals and the involvement of di-mu-oxyl radical bridged cobalt-iron centers as the active sites. These findings contribute to the understanding of bimetallic iron-containing OER catalysts.
ADVANCED ENERGY MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Hongyuan Yang, Gonela Vijaykumar, Ziliang Chen, J. Niklas Hausmann, Indranil Mondal, Suptish Ghosh, Victor C. J. Nicolaus, Konstantin Laun, Ingo Zebger, Matthias Driess, Prashanth W. Menezes
Summary: A well-defined helical iron borophosphate (LiFeBPO) is developed as an electro(pre)catalyst for the oxygen evolution reaction (OER) and selective alcohol oxidation. This catalyst exhibits exceptional OER performance and high selectivity for alcohol electrooxidation. In-situ and ex situ investigations reveal a deep reconstruction of LiFeBPO during OER, forming a 3D open porous skeleton assembled by ultrasmall, low-crystalline alpha-FeOOH nanoparticles.
ADVANCED FUNCTIONAL MATERIALS
(2023)
Article
Chemistry, Applied
Anna Hruzikova, Lucie Muzikova Cechova, Sille Stepanova, Lucie Tuckova, Marketa Tichotova, Ales Ruzicka, Vaclav Kasicka, Eliska Prochazkova
Summary: Azopyrimidines are a new class of photoswitches that can switch between trans and cis isomers. Their low solubility in water limits their biological applications, but this can be overcome by inclusion into supramolecular structures. Our research focuses on the structure, isomerization, and host-guest chemistry of azopyrimidines with cyclodextrins. We found that beta-cyclodextrin exhibits high selectivity for the accommodation of these compounds.
Article
Chemistry, Inorganic & Nuclear
Petr Svec, Iva Vranova, Zdenka Ruzickova, Maksim A. Samsonov, Libor Dostal, Ales Ruzicka
Summary: A series of organoantimony(III/V) and organobismuth(V) fluorides with a C,N-chelating ligand (L) were synthesized using LCNR2SnF and/or XeF2 as fluorinating agents. The compounds were characterized by elemental analysis, multinuclear solution NMR spectroscopy, and single crystal XRD analysis. The experimental results were supported by theoretical calculations. The preparation and structural characterization of LSbI2 were also reported. (c) 2023 Elsevier B.V. All rights reserved.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Changkai Shan, Shicheng Dong, Shenglai Yao, Jun Zhu, Matthias Driess
Summary: We report the successful synthesis and unique reactivity of the first divalent silicon species 3 supported by a chelating bis(N-heterocyclic silylene)bipyridine ligand. The compound was obtained by direct reaction of 1 with Idipp-SiI2 or by two-electron reduction of the corresponding Si(IV) precursor 2. Density functional theory calculations reveal that the lone pair on the ptSi(II) resides almost entirely in its 3pz orbital, distinguishing it from known four-coordinate silylenes. The reaction of 2 with [CuOtBu] leads to the regeneration of the bis(silylene) arms and the oxidation of the central Si(II) atom, forming the neutral bis(silylene)silyl Cu(I) complex 5.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Jan Zechovsky, Erik Kertesz, Milan Erben, Roman Jambor, Ales Ruzicka, Zoltan Benko, Libor Dostal
Summary: The reactivity of pnictinidenes towards substituted ortho- and para-quinones was studied. Ortho-quinones oxidized the central pnictogen atom, while in the case of arsenic compounds, a new azaarsole ring was formed. Heating these arsenic heterocycles resulted in a C-H bond activation and reductive elimination. Para-quinones also oxidized the central atom and led to hydrogen migration, with feasible reductive elimination.
Article
Chemistry, Multidisciplinary
Michael Schwarze, Steffen Borchardt, Marvin L. L. Frisch, Jason Collis, Carsten Walter, Prashanth W. W. Menezes, Peter Strasser, Matthias Driess, Minoo Tasbihi
Summary: Four commercial titanium dioxide photocatalysts were immobilized on steel plates and their performance in phenol degradation under UV-LED irradiation was investigated. The best result was obtained with the P90/UV/H2O2 system, achieving 100% degradation and around 70% mineralization after 3 hours of irradiation. The study highlights the importance of water quality for the photocatalytic performance.
Article
Chemistry, Multidisciplinary
Indranil Mondal, Pramod V. Menezes, Konstantin Laun, Thomas Diemant, Mohammad Al-Shakran, Ingo Zebger, Timo Jacob, Matthias Driess, Prashanth W. Menezes
Summary: A hierarchical amorphous birnessite-type manganese oxide layer was synthesized on 3D nickel foam using a rapid in-liquid plasma approach. The resulting catalyst exhibited high activity in oxygen evolution reaction (OER) and chemoselective dehydrogenation of benzylamine.
Review
Nanoscience & Nanotechnology
Suptish Ghosh, Basundhara Dasgupta, Carsten Walter, Prashanth W. Menezes, Matthias Driess
Summary: The ongoing challenge of developing efficient electrocatalysts for water-splitting has led to intense efforts in designing effective methods to improve electrocatalytic performances. The use of single-source (molecular) precursors (SSPs) has gained significant attention for their ability to create nanostructured materials with fine-tuned properties, resulting in high and stable catalytic activities.
Article
Chemistry, Inorganic & Nuclear
Jan Zechovsky, Vit Kremlacek, Milan Erben, Martin Hejda, Elena Rychagova, Roman Jambor, Ales Ruzicka, Sergey Ketkov, Libor Dostal
Summary: This paper reports the reactivity of two types of organopnictogen(I) N,C,N-pincer ligand coordinated compound towards an electron-deficient alkyne, dimethyl acetylenedicarboxylate (DMAD). The reactions show significant examples of element-ligand cooperation. The compounds react via dearomatization of a latent heteropnictole ring, producing rare examples of hetero Diels-Alder (DA) adducts. Furthermore, the study includes a theoretical survey to describe the main thermodynamic parameters and reaction pathways.
DALTON TRANSACTIONS
(2022)
