Article
Chemistry, Multidisciplinary
Estefania del Horno, Jesus Jover, Miguel Mena, Adrian Perez-Redondo, Carlos Yelamos
Summary: By reacting [TiCp*Cl-3] with magnesium, a trinuclear mixed-valence complex is formed, which can react with dinitrogen to produce a diamagnetic compound. The reaction process can potentially be used for cyclic ammonia synthesis under ambient conditions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Inorganic & Nuclear
Koh Sugamata, Teppei Asakawa, Mao Minoura
Summary: The synthesis and isolation of the first examples of a tetraselenolane and a hexaselenepane from the reaction of a bissilylcarbenoid with elemental selenium is reported. The molecular structures of these cyclic polyselenides were determined using X-ray diffraction analysis. Selective synthesis of these polyselenides was achieved by controlling the reaction temperature. Stoichiometric deselenation of the hexaselenepane yielded the tetraselenolane, while further deselenation of the tetraselenolane resulted in the formation of diselenirane.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Moritz Theodor Scharnhoelz, Peter Coburger, Lisa Gravogl, Daniel Klose, Juan Jose Gamboa-Carballo, Gregoire Le Corre, Jonas Boesken, Clara Schweinzer, Debora Thoeny, Zhongshu Li, Karsten Meyer, Hansjorg Gruetzmacher
Summary: In this study, a series of iron carbonyl complexes were synthesized and their electronic structures were analyzed. The complexes can be described as either electron precise or Wade-Mingos clusters.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Peter Coburger, Fabio Masero, Jonas Bosken, Victor Mougel, Hansjorg Grutzmacher
Summary: The reaction of imidazolium-substituted iphosphate-diide with GeCly dioxane and KBArF24 results in the formation of a rare dicationic spherical-aromatic nido-cluster. This complex undergoes two reversible one-electron reductions and rearranges to form 2D aromatic and planar structures. Oxidation of these planar species leads to the restoration of the 3D aromatic cluster.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Maximilian Muhr, Raphael Buhler, Hao Liang, Jonas Gilch, Christian Jandl, Samia Kahlal, Jean-Yves Saillard, Christian Gemel, Roland A. Fischer
Summary: Treatment of [Ru(COD)(MeAllyl)(2)] and [Ru(COD)(COT)] with GaCp* under hydrogenolytic conditions leads to the formation of reactive intermediates capable of activating Si-H or C-H bonds. The structures and properties of the resulting complex compounds [Ru(GaCp*)(3)(SiEt3)H-3] (1) and [Ru(GaCp*)(3)(C7H7)H-3] (2) have been investigated and characterized.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Review
Chemistry, Multidisciplinary
Yukatsu Shichibu, Katsuaki Konishi
Summary: This review introduces recent studies on the chirality of gold clusters, focusing on the geometric features of the ligand shells and the atomic-level origin of chiroptical activity. The findings from computational studies provide important insights into the chiral properties of gold clusters and can contribute to the design of chirality-controlled catalysts.
Article
Chemistry, Multidisciplinary
Lukasz Makolski, Vadim Szejko, Karolina Zelga, Adam Tulewicz, Piotr Bernatowicz, Iwona Justyniak, Janusz Lewinski
Summary: The synthesis and structural characterization of long sought-after structural forms of RZnOR' alkoxides, including a roof-like trimer and ladder-type tetramer, have been reported in this study. These novel aggregates exhibit robustness in the solid state and resistance to mechanical force. The use of H-1 NMR and diffusion-order spectroscopy demonstrated the kinetically labile nature of the new RZnOR' alkoxides in solution, highlighting their potential for ligand scrambling.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Lia Sotorrios, Fedor M. Miloserdov, Anne-Frederique Pecharman, John P. Lowe, Stuart A. Macgregor, Mary F. Mahon, Michael K. Whittlesey
Summary: The syntheses, reactivity, and electronic structure analyses of [Ru(PPh3)(2)(ZnMe)(4)H-2] and [Ru(PPh3)(2)(ZnPh)(4)H-2] are reported. [Ru(PPh3)(2)(ZnMe)(4)H-2] exhibits an 8-coordinate Ru center with axial phosphines and a symmetrical (2 : 2) arrangement of ZnMe ligands in the equatorial plane. The ZnMe ligands in [Ru(PPh3)(2)(ZnMe)(4)H-2] undergo facile, sequential exchange with ZnPh2 to give [Ru(PPh3)(2)(ZnPh)(4)H-2], which shows a 3 : 1 arrangement of ZnPh ligands. Mechanisms for ZnMe/ZnPh exchange and isomerization are proposed using DFT calculations, and the relationships of these {Ru(ZnR)(4)H-2} species to isoelectronic Group 8 transition metal polyhydrides and related Schlenk equilibria in the Negishi reaction are discussed.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Inorganic & Nuclear
Jonas Jablonski, Jonas Bresien, Martin Koeckerling
Summary: Research shows that a new metal cluster compound was obtained by reducing HfCl4 under ionothermal conditions using (BMIm)[AlCl4] as a solvent and reactant, containing nona-nuclear metalloid cluster units with an unprecedented arrangement of metal atoms. The compound is characterized by bridging of Hf-9 polyhedron edges by Cl atoms, with apical sites Cl-bonded to [AlCl4]- anions, forming 1D cluster strands. DFT calculations indicate significant metal-metal bonding and the presence of hydridic H atoms bridging triangular faces of the metal atom skeleton.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Lanchun Zhang, Ranyun Hu, Can Li, Yinyan Gong, Lengyuan Niu
Summary: The density functional theory calculations were used to investigate the Raman performances of stable CuAg and CuAu clusters for 4-NBT probe molecule. Suitable alloying designs in atomic level were found to reduce cost and enhance Raman signal of noble nanoparticles. The designed clusters exhibited enhanced Raman diffraction peak intensity beyond 11.0% compared to the 4-NBT molecule on the Ag4, Ag13 and Au13 clusters. This strategy could be applied to designing noble metal based surface-enhanced Raman materials with low cost and high enhancement ability by adjusting the atom site in atomic level.
CHEMICAL PHYSICS LETTERS
(2023)
Article
Materials Science, Multidisciplinary
A. Ektarawong, S. Khamkaeo, B. Alling, T. Bovornratanaraks
Summary: The mixing thermodynamics of antifluorite-structured Mg2Si1-xGex were investigated using first-principles calculations, revealing the ease of formation of single-phase random solid solutions of Mg2Si1-xGex from 50 K and above. At 0 K, there is a weak energy preference towards local phase segregation, while a small lattice misfit between Mg2Si and Mg2Ge contributes to the stable formation of Mg2Si1-xGex random solid solutions at low temperatures. These findings also suggest the thermodynamic and mechanical stability of these solid solutions, providing insight into the complete solubility of Mg2Ge in Mg2Si and vice versa at all temperatures where atomic diffusion is activated.
Article
Chemistry, Multidisciplinary
Lucas de Azevedo Santos, Teodorico C. Ramalho, Trevor A. Hamlin, F. Matthias Bickelhaupt
Summary: The study conducted a hierarchical benchmark and performance analysis of selenium bonds using ab initio and DFT methods. The results indicated that M06-2X, B3LYP, and M06 were the top-performing functionals, while BLYP-D3(BJ) and PBE showed poorer performance.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Yanbang Li, Thomas J. Emge, Antonio Moreno-Vicente, William P. Kopcha, Yue Sun, Iram F. Mansoor, Mark C. Lipke, Gene S. Hall, Josep M. Poblet, Antonio Rodriguez-Fortea, Jianyuan Zhang
Summary: A new multicomponent reaction involving isocyanide, alkynes, and endohedral metallofullerene (EMF) Lu3N@C-80 has been developed to yield metallofulleroids characterized by various analytical techniques. Single crystal studies revealed ordered Lu3N cluster in one ketenimine metallofulleroid, which is rare for EMF monoadducts. Computational analysis confirmed that the motion of the endohedral cluster is influenced by the position of exohedral organic appendants.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Wenjing Wang, Yong Deng, Xiumin Chen, Xuquan Wang, Zhongqian Zhao, Bingyang He, Hongyu Wang, Wei Li, Peilin Xu, Qi Yin
Summary: As the cluster size increases, the structure tends to be spherical, with In and Zn atoms dispersed in the system. The binding force of In-In and Zn-In bonds is stronger than that of Zn-Zn bonds. The nonmetallicity of clusters decreases while the metallicity increases with cluster size, and even clusters are more stable than odd clusters.
JOURNAL OF MOLECULAR STRUCTURE
(2022)
Article
Chemistry, Physical
Peng Zhang, Haobin Tan, Zhongkai Wang, Lai Lyu, Chun Hu
Summary: Establishing structure-activity relationship is crucial for designing catalysts with low energy consumption and high efficiency in advanced oxidation processes. This study investigates the atomic mechanism of hydrogen peroxide dissociation and formation on different zinc chalcogenides. The catalytic activity of hydrogen peroxide on zinc chalcogenides is determined by the surface micro-engineering construction including surface orientation and heteroatomic doping. These findings not only provide a better understanding of the mechanism of hydrogen peroxide on zinc chalcogenides, but also offer guidance for the development of new catalytic oxidation systems.
APPLIED SURFACE SCIENCE
(2023)
Review
Chemistry, Physical
Weijin Li, Soumya Mukherjee, Baohui Ren, Rong Cao, Roland A. Fischer
Summary: Open framework materials (OFMs) in the form of thin films have great potential as electrocatalysts, but their development is still in its early stages, with a need for further research. Controlling the thickness, roughness, and particle sizes of the films is crucial for their electrocatalytic activities.
ADVANCED ENERGY MATERIALS
(2022)
Article
Chemistry, Multidisciplinary
Anna Lisa Semrau, Philip M. Stanley, Dominik Huber, Michael Schuster, Bauke Albada, Han Zuilhof, Mirza Cokoja, Roland A. Fischer
Summary: Vectorial catalysis, controlling multi-step reactions in a programmed sequence with defined spatial localization, is a challenging goal in bio-inspired catalysis research. This study demonstrates the integration of two different surface-anchored nanometer-sized metal-organic frameworks in a microfluidic device for modeling vectorial catalysis, achieving full conversion and high turnover frequencies in a two-step cascade reaction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Physical
Haneesh Saini, Eva Otyepkova, Andreas Schneemann, Radek Zboril, Michal Otyepka, Roland A. Fischer, Kolleboyina Jayaramulu
Summary: Oil contaminated water is a global issue, and metal-organic frameworks (MOFs) with special wettability show promising potential for oil/water separation. Their highly tunable structure and properties make them suitable for various applications in oily water treatment.
JOURNAL OF MATERIALS CHEMISTRY A
(2022)
Review
Electrochemistry
Soumya Mukherjee, Shujin Hou, Sebastian A. Watzele, Batyr Garlyyev, Weijin Li, Aliaksandr S. Bandarenka, Roland A. Fischer
Summary: Taking into account the United Nations Sustainable Development Goal 7 on affordable and clean energy, metal-organic frameworks (MOFs) and derived materials have attracted research interest in electrocatalysis. This review summarizes recent advances in MOF-based electrocatalysts exclusively prepared through indirect post-treatments.
Review
Electrochemistry
Xing Ding, Theophilus Kobina Sarpey, Shujin Hou, Batyr Garlyyev, Weijin Li, Roland A. Fischer, Aliaksandr S. Bandarenka
Summary: Understanding processes, phenomena, and mechanisms at the electrode/electrolyte interface is crucial for optimizing electrochemical systems. The introduction of sub-microsecond laser pulses has simplified the investigation of the electrochemical interface, and the laser-induced current transient and laser-induced potential transient techniques have proven to be valuable tools.
Article
Chemistry, Multidisciplinary
Shujin Hou, Lili Xu, Xing Ding, Regina M. Kluge, Theophilus Kobina Sarpey, Richard W. Haid, Batyr Garlyyev, Soumya Mukherjee, Julien Warnan, Max Koch, Shengli Zhang, Weijin Li, Aliaksandr S. Bandarenka, Roland A. Fischer
Summary: Understanding the electrode/electrolyte interface is crucial for optimizing electrocatalytic performances. The nature of alkali metal cations has been found to have a profound impact on the oxygen evolution activity of SURMOF derived electrocatalysts based on NiFe(OOH). The effects of cation-dependent electric double layer properties on activity were studied using a laser-induced current transient technique. Electrolyte composition can be used to maximize the performance of SURMOF derivatives in electrochemical water splitting.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Crystallography
Rudiger W. Seidel, Iris M. Oppel
Summary: Two bismuth(III) coordination polymers were synthesized and structurally characterized, showing 2D honeycomb layers with (6,3) topology. The layers are stacked along the [001] direction, forming virtually hexagonal channels occupied by disordered methanol and water molecules. The potential solvent area per unit cell volume is 42.2% for 1 and 44.0% for 2.
JOURNAL OF CHEMICAL CRYSTALLOGRAPHY
(2023)
Article
Crystallography
Adrian Richter, Richard Goddard, Peter Imming, Ruediger W. Seidel
Summary: The structure of a new compound was successfully synthesized and determined. X-ray crystallography revealed that the compound is composed of two benzothiazinone moieties linked by a Z-configured azoxy group, forming a densely packed herringbone pattern in the crystal.
ACTA CRYSTALLOGRAPHICA SECTION E-CRYSTALLOGRAPHIC COMMUNICATIONS
(2022)
Article
Chemistry, Medicinal
Markus Lang, Uday S. Ganapathy, Lea Mann, Rana Abdelaziz, Rudiger W. Seidel, Richard Goddard, Ilaria Sequenzia, Sophie Hoenke, Philipp Schulze, Wassihun Wedajo Aragaw, Rene Csuk, Thomas Dick, Adrian Richter
Summary: This study describes the derivatization of MMV688845 by introducing a thiomorpholine moiety, and the preparation of the corresponding sulfones and sulfoxides. The molecular structures of three analogs are confirmed by X-ray crystallography, and the essential R configuration is proven to be conserved during synthesis. All analogs are characterized in a MIC assay against various mycobacteria, and the sulfone derivatives exhibit lower MIC90 values and higher aqueous solubility compared to the hit compound. The most potent derivatives possess bactericidal activity against Mycobacterium abscessus without being cytotoxic to mammalian cell lines.
JOURNAL OF MEDICINAL CHEMISTRY
(2023)
Article
Chemistry, Organic
Adrian Richter, Richard Goddard, Fabienne Siersleben, Lea Mann, Ruediger W. Seidel
Summary: Trehalose conjugates of 3-hydroxychromone (3HC) dyes have been used for fluorescence labeling to detect metabolically active mycobacteria, and the preferred conformation of 3HC-2 is s-cis. The crystal structure reveals the s-cis conformation and the supramolecular structure features hydrogen-bonded dimers and π…π stacking. Fluorescence microscopy shows that the non-pathogenic M. aurum can be labeled with the fluorescence probe 3HC-2-Tre for drug screening.
Article
Chemistry, Physical
Ruediger W. Seidel, Richard Goddard, Nils Noethling, Tsonko M. Kolev
Summary: The crystal and molecular structures of free-base lepidine and its mineral acid salts have been investigated. The stacking arrangement of the molecules and cations were elucidated, as well as the involvement of nitrogen atoms in intermolecular interactions. Hydrogen bonding between the salts and lepidinium cations was observed. Hirshfeld surface analysis provided insights into the packing arrangements of the salts.
JOURNAL OF MOLECULAR STRUCTURE
(2023)
Article
Chemistry, Multidisciplinary
Ruediger W. Seidel, Adrian Richter, Richard Goddard, Peter Imming
Summary: This article provides a comprehensive account of a potential new class of drugs for tuberculosis treatment called 8-nitro-4H-benzo[e][1,3]thiazin-4-ones. These compounds are potent antitubercular agents with a novel mechanism of action. The review includes synthesis, structures and reactivity, mechanism of action, in vitro activity and structure-activity relationships, as well as physicochemical and pharmacokinetic properties. It also summarizes in vivo models and clinical studies, addressing bioavailability issues and the challenge of potentially toxic nitroaromatic moiety, and suggests possible directions for further research through chemical modification.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Patricia Heiss, Julius Hornung, Christian Gemel, Roland A. Fischer
Summary: The formation of Hume-Rothery-inspired intermetallic and all-hydrocarbon-ligated Ni/E clusters (E = Al, Ga) was studied using a combinatorial, coordination-modulated approach. Insight into the chemical complexity generated during cluster nucleation and growth was obtained through mass spectrometric monitoring of the reaction solutions.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Zhiying Fan, Lena Staiger, Karina Hemmer, Zheng Wang, Weijia Wang, Qianjie Xie, Lunjia Zhang, Alexander Urstoeger, Michael Schuster, Johannes A. Lercher, Mirza Cokoja, Roland A. Fischer
Summary: The embedding of metal nanoparticles in metal-organic frameworks (MOFs) is crucial in catalysis research, as it prevents agglomeration and allows for functionalization of the MOF matrix to optimize the chemical environment. In this study, Pd nanoparticles were incorporated into the MOF CuBTC by encapsulation, and the hydrophobicity was adjusted by using functionalized linkers. These modifications significantly improved the catalytic activity, suggesting that channel engineering is an efficient way to optimize metal@MOF catalysts.
CELL REPORTS PHYSICAL SCIENCE
(2022)
Article
Chemistry, Physical
Adrian Richter, Michael Patzer, Richard Goddard, Julia B. Lingnau, Peter Imming, Rudiger W. Seidel
Summary: The study reports the crystal structure of a chiral compound BTZ043, which is a potential antitubercular drug candidate, and analyzes its molecular conformation and rotational barrier. The results show that the rotation of this compound is influenced by two barriers.
JOURNAL OF MOLECULAR STRUCTURE
(2022)
