Review
Chemistry, Inorganic & Nuclear
Alec Bigness, Shivaiah Vaddypally, Michael J. Zdilla, Jose L. Mendoza-Cortes
Summary: Heterocubane is a molecular species with a cube-shaped core found in nature, playing a crucial role in important biological reactions. Limited reviews have focused on the significance of the cluster outside of biology, or on the impact of the global coordination environment on reactivity and electronic structure. Understanding the synthetic chemistry of heterocubanes in the context of coordination environment and geometry offers insights into their connection to natural systems.
COORDINATION CHEMISTRY REVIEWS
(2022)
Article
Chemistry, Multidisciplinary
Youngsuk Kim, Arun Sridharan, Daniel L. M. Suess
Summary: This study reports the synthesis of a three-member series of isostructural mononitrosylated [Fe4S4] clusters and reveals the significance of mononitrosylated intermediates in NO sensing/signaling.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Justin T. Henthorn, George E. Cutsail, Thomas Weyhermueller, Serena DeBeer
Summary: This article investigates the electronic structure and spin states of mixed-valent iron-sulfur dimers and discovers a new interaction that can stabilize high spin states. By studying a series of mixed-valent complexes, complex interactions between antiferromagnetic coupling, Heisenberg double-exchange, and vibronic coupling are revealed.
Article
Chemistry, Multidisciplinary
Gayathri Kolliyedath, Tuhin Sahana, Silpa Mary Johnson, Subrata Kundu
Summary: (Per)thionitrite (SNO-/SSNO-) intermediates play important roles in modulating nitric oxide (NO) and hydrogen sulfide (H2S) dependent bio-signalling processes. This study reveals that stable thiocarbonyl compounds can react with nitrite anion to yield SNO-/SSNO-. The presence of both NO2- and thiocarbonyl motifs in the biological context suggests their synergistic activation leading to the generation of NO gas and various reactive sulfur species via SNO-/SSNO-.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Eranga H. Gamage, Saeed Kamali, Judith K. Clark, Yongbin Lee, Philip Yox, Padraic Shafer, Alexander A. Yaroslavtsev, Liqin Ke, Michael Shatruk, Kirill Kovnir
Summary: A novel mixed-valent hybrid chiral and polar compound, Fe7As3Se12(en)(6)(H2O), has been synthesized and characterized. The compound shows magnetic polarizability, but complete magnetic ordering is not achieved even at low temperatures. Computational analysis reveals competing ferrimagnetic ordered models within the chains.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Zhaoyang Chen, Huan Niu, Jie Ding, Heng Liu, Pei-Hsuan Chen, Yi-Hsuan Lu, Ying-Rui Lu, Wenbin Zuo, Lei Han, Yuzheng Guo, Sung-Fu Hung, Yueming Zhai
Summary: In this study, sulfur-doped Fe-1-NC catalyst was found to exhibit superior activity towards ORR compared to traditional Fe-NC materials. The incorporation of sulfur in the second coordination sphere of Fe-1-NC was shown to induce a transition of spin polarization configuration, with the low spin single-Fe3+-atom identified as the active site for ORR through operando Fe-57 Mossbauer spectra. Additionally, DFT calculations revealed that the lower spin state of the Fe center after sulfur doping promotes the OH* desorption process.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Biochemistry & Molecular Biology
Luca Valer, Daniele Rossetto, Taylor Parkkila, Lorenzo Sebastianelli, Graziano Guella, Amber L. Hendricks, James A. Cowan, Lingzi Sang, Sheref S. Mansy
Summary: Iron-sulfur clusters are believed to be ancient cofactors that may have played a role in early protometabolic systems. This study investigates the properties of peptides containing cysteine and histidine ligands and their ability to coordinate [2Fe-2S] clusters, comparing them to purified iron-sulfur proteins. The findings suggest that these complexes may have been important for early cell-like systems.
Article
Chemistry, Multidisciplinary
Andrea Capucciati, Enrico Monzani, Michela Sturini, Stefania Nicolis, Fabio A. Zucca, Luigi Bubacco, Marco Bortolus, Luigi Zecca, Luigi Casella
Summary: The study uses water-soluble melanin-protein-Fe/Cu conjugates derived from norepinephrine and fibrillar beta-lactoglobulin as reliable models for human brain locus coeruleus neuromelanin (NM). Iron and copper promote catecholamine oxidation and tend to remain coupled in oligonuclear aggregates. The Fe-Cu clusters are EPR silent and affect the H-1 NMR spectra of the conjugates.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Inorganic & Nuclear
Frank Stegemann, Theresa Block, Steffen Klenner, Yuemei Zhang, Boniface P. T. Fokwa, Carsten Doerenkamp, Hellmut Eckert, Oliver Janka
Summary: Eu2Ni8Si3 and Sr2Pt3Al8 were synthesized from the elements, crystallizing in different structures with distinct magnetic properties. Eu2Ni8Si3 exhibits a ferromagnetic transition and intermediate valence, while Sr2Pt3Al8 shows temperature independent magnetic susceptibility.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Alejandro Cadranel, Lisa Gravogl, Dominik Munz, Karsten Meyer
Summary: This study reports high-valent iron complexes supported by N-heterocyclic carbene (NHC)-anchored, bis-phenolate pincer ligands that undergo ligand-to-metal charge transfer (LMCT) upon photoexcitation. The excited states exhibit a ligand-based, mixed-valence system and intense intervalence charge transfer bands in the near-infrared region. The observations provide insight into the excited-state decay mechanism in high-valent NHC complexes.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Maria Drosou, Georgia Zahariou, Dimitrios A. Pantazis
Summary: The study reveals that the tetramanganese-calcium cluster of the oxygen-evolving complex in photosystem II adopts orientational Jahn-Teller isomeric forms in the resting state, which explains previous spectroscopic observations and establishes the functional role of this isomerism in the catalytic process.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Georgia Zahariou, Nikolaos Ioannidis, Yiannis Sanakis, Dimitrios A. Pantazis
Summary: The study reveals the importance of the S-3 state in the water-oxidizing Mn4CaO5 cluster of PSII, as it binds a substrate and precedes O-2 evolution. Methanol-treated PSII shows a previously uncharacterized high-spin species, coexisting with the known intermediate-spin conformation. These results provide insights into the structural heterogeneity of the S-3 state and offer constraints on the S-3 to S-4 transition and the mechanism of O-O bond formation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Multidisciplinary Sciences
Aidin R. Balo, Alessio Caruso, Lizhi Tao, Dean J. Tantillo, Mohammad R. Seyedsayamdost, R. David Britt
Summary: Using electron paramagnetic resonance (EPR) spectroscopy, this study dissected the mechanism of SuiB and revealed the essential role of the auxiliary [4Fe-4S] cluster in catalysis, confirming the proposed radical electrophilic aromatic substitution (rEAS) mechanism for the formation of the Lys-Trp cross-link. The findings provide direct evidence for the involvement of the SPASM domain auxiliary cluster and support rEAS as the mechanistic paradigm for rSAM enzyme-catalyzed carbon-carbon bond-forming reactions.
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2021)
Article
Chemistry, Multidisciplinary
Arun Sridharan, Alexandra C. Brown, Daniel L. M. Suess
Summary: This study reports the synthesis and characterization of the first terminal imido complex of an Fe-S cluster, demonstrating competency for C-H activation. The Fe-imido site is described as a high-spin Fe3+ center, with a long Fe-N(imido) distance of 1.763(2) angstrom.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Matic Lozinsek, Helene P. A. Mercier, Gary J. Schrobilgen
Summary: The coordination chemistry of KrF2 is limited compared to XeF2, but in this study, new mixed krypton/xenon compounds were synthesized where KrF2 acts as a ligand coordinating to xenon atoms. This extends the XeF2-KrF2 analogy and introduces a new class of coordination compound.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Yang Liu, Stefan G. G. Resch, Haowei Chen, Sebastian Dechert, Serhiy Demeshko, Eckhard Bill, Shengfa Ye, Franc Meyer
Summary: This article describes a flexible macrocyclic ligand that can host two Cu ions in reversibly interconvertible states. The complexes were characterized using various spectroscopic methods and calculations. The electron self-exchange between the two states is rapid despite structural reorganization and is proposed to proceed via an active conformer. This redox couple is unique and achieves fast electron self-exchange similar to the function of the Cu-A site.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Jianfeng Wu, Fan Zhang, Guo-Lu Wang, Serhiy Demeshko, Sebastian Dechert, Yi-Quan Zhang, Franc Meyer
Summary: Using a novel tricompartmental hydrazone ligand, a set of trinuclear Dy-3 complexes with different anions (Cl-, Br-, or ClO4-) and co-ligands were isolated and characterized. The magnetic properties of these complexes vary due to structural disorder and different relaxation processes, with Dy-3 center dot ClO4 showing the most robust magnetic behavior. The magneto-structural relationships were analyzed and rationalized using CASSCF/RASSI-SO calculations.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Sheida Rajabi, Franziska Ruettger, Jana Luecken, Sebastian Dechert, Michael John, Franc Meyer
Summary: Two mononuclear ruthenium(II) complexes with dianionic {N-4} ligands and axial pyridines were prepared and characterized structurally. The redox properties of the complexes were investigated electrochemically, and their potential as water oxidation catalysts was tested using cerium ammonium nitrate at pH 1.0. Complex 1 underwent degradation, likely due to ligand oxidation, while complex 2 exhibited higher stability and efficiency in water oxidation reactions.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Kui Zeng, Claudia Stueckl, Jie Qin, Martin Simon, Can-Jerome Spyra, Jun Li, Franc Meyer, Kai Zhang
Summary: This article reports a highly efficient iodoarene-mediated aerobic oxidation method for carboxylic acids in aqueous phase, which provides access to a large number of carboxylic acids containing aromatic aldehydes and saturated/unsaturated aliphatic aldehydes. Detailed mechanistic studies provide strong evidence for the interception of hypervalent iodine intermediates through aldehyde hydrate.
MOLECULAR CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Luisa Maria Gatzemeier, Franc Meyer, Ulf Diederichsen, Tiago Fleming Outeiro
Summary: Alpha-Synuclein is a protein involved in neurodegenerative disorders that accumulate in brain protein inclusions. We have developed a chemical synthesis method for Alpha-Synuclein, allowing the synthesis of protein variants for further investigation of its structure and aggregation behavior.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Ruth Weller, Mihail Atanasov, Serhiy Demeshko, Ting-Yi Chen, Ivan Mohelsky, Eckhard Bill, Milan Orlita, Franc Meyer, Frank Neese, C. Gunnar Werncke
Summary: The magnetic properties of linear iron(I) silylamides K{crypt}[FeL2] and [KFeL2] were investigated. Slow-relaxation of magnetization, magnetic hysteresis, and magnetic blocking were observed in K{crypt}[FeL2]. In [KFeL2], with increased axial anisotropy, higher relaxation barrier and blocking temperature were observed, in agreement with field-dependent IR-spectroscopy, magnetic measurements, and theoretical analysis.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Jakob Steube, Ayla Kruse, Olga S. Bokareva, Thomas Reuter, Serhiy Demeshko, Roland Schoch, Miguel Arguello A. Cordero, Athul Krishna, Stephan Hohloch, Franc Meyer, Katja Heinze, Oliver Kuehn, Stefan Lochbrunner, Matthias Bauer
Summary: This study presents a luminescent iron compound that exhibits dual emission behavior from ligand-to-metal charge transfer (LMCT)- and metal-to-ligand charge transfer (MLCT)-dominated states. The compound has a unique ligand design that enables the presence of energetically accessible MLCT states, providing potential for electron transfer reactions in photoredox catalysis.
Article
Chemistry, Inorganic & Nuclear
Andres Gonzalez, Ting-Yi Chen, Serhiy Demeshko, Franc Meyer, C. Gunnar Werncke
Summary: We report the synthesis of a linear N-heterocyclic carbene (NHC)-based chromium(I) silylamide and its magnetic properties. The compound [(IMes)Cr(N{Dipp}SiiPr3)] was obtained through protolytic ligand displacement, and the method was also extended to a bulkier NHC IDipp. Further reactions of the chromium(I) complex yielded different coordination compounds such as a chromium dicarbonyl complex and a chromium bromide complex.
Article
Chemistry, Physical
Tim P. Schlachta, Greta G. Zambo, Michael J. Sauer, Isabelle Rueter, Carla A. Hoefer, Serhiy Demeshko, Franc Meyer, Fritz E. Kuehn
Summary: A comparative study was conducted to investigate the influence of electronic variations on the catalytic performance of three iron(II) NHC epoxidation catalysts. Different ligands were used to prepare the complexes, which were characterized using various methods. The results showed that a lower electron density at the iron atom led to a decline in epoxidation activity, while a more electron rich iron center did not necessarily result in higher activity due to reduced catalyst stability. Addition of Lewis acids significantly improved both activity and stability of the catalysts.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Yang Liu, Sayanti Chatterjee, George E. Cutsail III, Sergey Peredkov, Sandeep K. Gupta, Sebastian Dechert, Serena DeBeer, Franc Meyer
Summary: This study reports the synthesis and characterization of [Cu-4(& mu;(4)-S)](n+) (n = 2, 2; n = 3, 3) clusters, which mimic the two active states of the Cu-Z* site during enzymatic N2O reduction. The structural and electronic properties of these clusters are elucidated using multiple methods. Preliminary reactivity studies demonstrate the nucleophilic character of the central & mu;(4)-S in the fully reduced 0-hole state.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Inorganic & Nuclear
Jose de Jesus Velazquez-Garcia, Krishnayan Basuroy, Darina Storozhuk, Joanne Wong, Serhiy Demeshko, Franc Meyer, Robert Henning, Simone Techert
Summary: This study investigates the structural evolution of a defect [2 x 2] triiron(II) metallogrid during temperature increase and light irradiation. The flexibility of the grid leads to interesting characteristics that can be used for intermolecular cooperativity in related thermally responsive systems. The time-resolved photocrystallography reveals the photoinduced and elastic steps in the out-of-equilibrium process.
DALTON TRANSACTIONS
(2023)
Article
Materials Science, Multidisciplinary
Weiyang Li, Aurelian Rotaru, Mariusz Wolff, Serhiy Demeshko, Franc Meyer, Yann Garcia
Summary: By symmetric modification of the ligand architecture, two iron-based complexes were constructed as colorimetric NH3(g) sensors, which showed a remarkable colour change from reddish brown or light purple to dark grey at room temperature. One of the complexes presented a shorter response time due to its empty cage structure and large specific surface area increasing the adsorption rate of NH3(g).
JOURNAL OF MATERIALS CHEMISTRY C
(2023)
Article
Chemistry, Multidisciplinary
Sandeep K. Gupta, Shashank V. Rao, Serhiy Demeshko, Sebastian Dechert, Eckhard Bill, Mihail Atanasov, Frank Neese, Franc Meyer
Summary: Understanding the effects of the local coordination environment and ligand field on magnetic anisotropy is crucial for controlling the magnetic properties of single-ion magnets (SIMs). In this study, a series of tetracoordinate cobalt(ii) complexes with electron-withdrawing -C6F5 substituents were synthesized and their magnetic properties were investigated. The results showed that the dihedral twist angle between the chelate planes in the solid state greatly influenced the magnetic properties, and the energy gaps of electronic transitions were correlated with the zero-field splitting (ZFS) parameter.
Article
Chemistry, Inorganic & Nuclear
Gargi Bhatt, Tanu Sharma, Sandeep K. Gupta, Franc Meyer, Gopalan Rajaraman, Ramaswamy Murugavel
Summary: In this study, the single-ion magnetic (SIM) behavior of three mononuclear cobalt-(II) tetrahedral complexes was examined. The variation in the dynamic magnetic properties of the Co-(II) ion in a tetrahedral ligand field was studied by changing the halide ligand. The ab initio CASSF calculations matched well with the experimental data, revealing the influence of halide ions on the axial zero-field splitting parameter D.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Andres Gonzalez, Serhiy Demeshko, Franc Meyer, C. Gunnar Werncke
Summary: A labile iron organoazide adduct that undergoes dissociation equilibrium and intramolecular C-H bond amination in solution is reported. Single-crystal irradiation of the azide led to the formation of a putative imido iron intermediate, identified as a highly covalent {FeNR}8 species computationally.
CHEMICAL COMMUNICATIONS
(2023)
