Article
Chemistry, Multidisciplinary
Sota Funaki, Tokuhisa Kawawaki, Tomoshige Okada, Kana Takemae, Sakiat Hossain, Yoshiki Niihori, Takumi Naito, Makito Takagi, Tomomi Shimazaki, Soichi Kikkawa, Seiji Yamazoe, Masanori Tachikawa, Yuichi Negishi
Summary: The geometric/electronic structure of tiara-like metal nanoclusters [Ni-n(PET)(2n); n = 4, 5, 6, where PET refers to phenylethanethiolate] with the same SR ligand was evaluated. The geometric structure of Ni-5(SR)(10) was determined for the first time using single-crystal X-ray diffraction. Additionally, combined electrochemical measurements and X-ray absorption fine structure measurements revealed that Ni-5(SR)(10) easily forms an OER intermediate and therefore exhibits a high specific activity.
Article
Chemistry, Inorganic & Nuclear
Akram Ali, Saumitra Bhowmik, Suman K. Barman, Narottam Mukhopadhyay, Christine E. Glueer (nee Schiewer), Francesc Lloret, Franc Meyer, Rabindranath Mukherjee
Summary: This study synthesized and characterized a green complex 1 with important redox activity. The study found two oxidative and one reductive redox processes in 1 and determined the electronic states of the ligand and metal. The study also discovered a thermally driven valence-tautomeric equilibrium in 1.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
J. L. S. Milani, A. F. P. Biajoli, F. I. Batista, R. S. Oliboni, O. L. Casagrande
Summary: A series of new Cr(III) complexes were successfully synthesized and showed moderate activity in ethylene oligomerization, with a uniform distribution of oligomers and polymer production ranging from 1.2% to 9.8%. The catalytic activity is mainly controlled by electronic effects at the thioether/imine groups.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Physical
Valentina Migliorati, Giuseppe Fazio, Simone Pollastri, Alessandra Gentili, Pierpaolo Tomai, Francesco Tavani, Paola D'Angelo
Summary: This study utilizes a synergic approach combining XANES, EXAFS spectroscopies, and QM calculations to investigate the solvation properties of HgCl2 and HgO in DESs. The experimental results show that Hg2+ forms a tetrahedral complex with four chloride ions in DESs, indicating strong interactions between Cl- anions and Hg2+.
JOURNAL OF MOLECULAR LIQUIDS
(2021)
Article
Materials Science, Ceramics
Jakkree Boonlakhorn, Bundit Putasaeng, Pinit Kidkhunthod, Jedsada Manyam, Sriprajak Krongsuk, Pornjuk Srepusharawoot, Prasit Thongbai
Summary: By doping Sn4+, high dielectric permittivity and low loss tangent were achieved in CaCu2.95Mg0.05Ti4O12 ceramics, along with improvements in breakdown electric field and nonlinear coefficient. Reduction in the Cu+/Cu2+ ratio led to increased resistivities of grains and grain boundaries, resulting in improved nonlinear electrical properties.
JOURNAL OF THE EUROPEAN CERAMIC SOCIETY
(2021)
Article
Chemistry, Organic
Linhua Wang, Xuesong Zheng, Qinze Zheng, Zhenlong Li, Jian Wu, Ge Gao
Summary: A Cu-catalyzed regioselective C5-H arylation of imidazo[1,5-a]pyridines with aryl iodides was achieved with the assistance of an ethylthio group at the C3 position. This directing group could be easily removed to produce a range of 5-(hetero)arylimidazo[1,5-a]pyridine derivatives. The reaction tolerates various functionalities and is compatible with sterically hindered substrates.
Article
Geochemistry & Geophysics
Lijie Zhang, Xujun Liang, Quanying Wang, Yaoling Zhang, Xiangping Yin, Xia Lu, Eric M. Pierce, Baohua Gu
Summary: This study investigated the isotope exchange between newly spiked and pre-existing Hg(II) in environmental matrices, as well as its impact on Hg(II) transformation and bioaccumulation. The results suggest that isotope exchange may lead to biased rate calculations of Hg(II) transformation and bioaccumulation when enriched Hg isotopes are applied in environmental matrices.
GEOCHIMICA ET COSMOCHIMICA ACTA
(2021)
Article
Chemistry, Inorganic & Nuclear
Sanya Pachisia, Ram Kishan, Samanta Yadav, Rajeev Gupta
Summary: This study reports the synthesis and characterization of two half-sandwich Ru(II) complexes supported with amide-phosphine based ligands, which serve as significant catalysts for the borohydride mediated reduction of various nitro-substrates. Mechanistic studies have confirmed the intermediacy of [Ru-H] in the reduction and asserted the involvement of several organic intermediates during the catalysis.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Nikita M. Ankudinov, Denis A. Chusov, Yulia Nelyubina, Dmitry S. Perekalin
Summary: A new method for synthesizing chiral diene rhodium catalysts has been introduced, with one catalyst showing efficient asymmetric insertion of diazoesters into B-H and Si-H bonds with high yields and enantiomeric purity. The stereoselectivity of separation and catalytic reaction can be predicted by DFT calculations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Inorganic & Nuclear
Man-Man Xue, Jiarui Chang, Jie Zhang, Xuenian Chen
Summary: In this study, two types of platinum thiolate complexes were successfully synthesized and fully characterized. The results showed that these platinum complexes exhibited high catalytic activity in the hydrosilylation of aldehydes and ketones. Additionally, the catalytic system showed good compatibility with the subsequent hydrolysis reaction.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Physical
Jinfeng Yang, Zhaoyu Yang, Xiaonan Wang, Yuxiang Chen, Yongze Xu, Bo Zou, Yuli Yan, Huarui Sun
Summary: In this study, Zintl-phase TiNiSi-type SrMgSi and CaMgGe with low intrinsic lattice thermal conductivity were investigated for thermoelectric applications. The low thermal conductivity is attributed to the strong lattice anharmonicity and optical-acoustic phonon coupling, while the high band degeneracy leads to good electrical properties. The predicted ZT values for SrMgSi and CaMgGe were 2.83 and 3.09, respectively.
ACS APPLIED ENERGY MATERIALS
(2023)
Article
Chemistry, Inorganic & Nuclear
Francesco Caddeo, Vanesa Fernandez-Moreira, Massimiliano Arca, Anna Pintus, Antonio Laguna, Vito Lippolis, M. Concepcion Gimeno
Summary: The coordination modes of ligand 2,5,8-trithia[9](2,6)pyridinophane (L) with thallium(i), gold(iii), and gold(i) were studied, revealing distinct coordination patterns and geometries in the complexes. Additionally, the complex exhibited interesting thermochromic behavior with emission spectra showing different characteristics at room temperature and 77 K, possibly due to the different thallium environments. Furthermore, DFT calculations were conducted to investigate the emission origins of the complex.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Multidisciplinary
Guanping Li, Olaf Stefanczyk, Kunal Kumar, Yuuki Mineo, Koji Nakabayashi, Shin-ichi Ohkoshi
Summary: In this study, six new high-dimensional frameworks were successfully synthesized by self-assembly of Fe-II complexes of phenazine, quinoxaline, and 4,4'-trimethylenedipyridine with tetrahedral building blocks of [Hg-II(XCN)(4)](2-) (X=S or Se). Compounds 1, 3, and 3-Se exhibited intense sub-terahertz (sub-THz) absorbance, while compounds 1, 4, and 4-Se showed low-frequency Raman scattering. These findings suggest that heavy metal Fe-II-Hg-II systems are promising platforms for constructing sub-THz absorbers.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Inorganic & Nuclear
Ashok Kumar, Rohit Gupta, Ganesan Mani
Summary: A one-pot reaction was conducted between ethylenediamine, paraformaldehyde, and Ph2PH or tBu2PH, yielding a new diphosphine compound, 1,3-bis((diphenylphosphanyl)methyl)imidazolidine L1 or 1,3-bis((di-tert-butylphosphanyl)methyl)imidazolidine L2, respectively, with high yields. Metalation of L1 and L2 with [NiCl2(DME)] in the presence of KPF6 resulted in the formation of pincer carbene nickel chloride complexes, [(PhPCP)NiCl]PF6 and [(tBuPCP)NiCl]-PF6, through simultaneous double C-H bond activations. The thiolate complexes, [(PhPCP)Ni(SPh)2], [(PhPCP)NiSPh]PF6, and [(tBuPCP)NiSPh]PF6, produced by the reaction of 1 and 2 with PhSNa acted as efficient catalysts for the hydrosilylation of aldehydes, ketones, and nitroarenes.
Article
Chemistry, Inorganic & Nuclear
Dongwon Kim, Junmyeong Park, Gyeongwoo Kim, Soojin Lee, Mohammad Mozammal Hossain, Ok-Sang Jung
Summary: A pair of chiral cages were self-assembled using symmetric chiral ligands, and could be downsized with the presence of hydrochloric acid. The original cages showed better enantioselectivity for chiral recognition, while the downsized cages exhibited significant recognition of chiral molecules through photoluminescence.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Artem Svyazhin, Vladimir Nalbandyan, Mauro Rovezzi, Aleksandra Chumakova, Blanka Detlefs, Alexander A. Guda, Alessandro Santambrogio, Alain Manceau, Pieter Glatzel
Summary: X-ray spectroscopy using high-energy-resolution fluorescence detection (HERFD) provides detailed information on the oxidation state, phase composition, and local environment in molybdenum-based compounds at the L-3-edge. The chemical shift of HERFD L-3-edge spectra follows a parabolic dependence on the oxidation state, providing insights into the distortion of ligand environments and radial order of atoms around the absorber. The comparison of high-resolution spectra with theoretical simulations demonstrates the ability of the single-electron approximation to reproduce the spectral shape accurately, which can be useful in various fields including physics, chemistry, materials science, and biochemistry.
INORGANIC CHEMISTRY
(2022)
Article
Polymer Science
Gabriel Marineau-Plante, Malak Qassab, Adrien Schlachter, Melodie Nos, Muriel Durandetti, Julie Hardouin, Cyprien Lemouchi, Loic Le Pluart, Pierre D. Harvey
Summary: In this study, platinum(II) polyyne/diketopyrrolopyrole-containing polymers of different chain lengths were prepared to investigate the reasons for the poor photoconversion efficiencies observed in previous research. Through thermodynamic arguments, quenching experiments, and photochemical stability testing, it was found that the undetected photochemical instability of similar polymers and the inappropriate choice of electron acceptor may contribute to the lower efficiencies.
JOURNAL OF INORGANIC AND ORGANOMETALLIC POLYMERS AND MATERIALS
(2022)
Article
Materials Science, Multidisciplinary
M. Salaun, A. D. Sontakke, V Maurel, J. M. Mouesca, A. L. Barra, V. F. Guimaraes, V Montouillout, B. Viana, I Gautier-Luneau, A. Ibanez
Summary: The study investigates the structural, spectroscopic, and optical properties of glassy yttrium and aluminum borate powders. The photoluminescence emissions are attributed to the large polyaromatic molecules generated during thermal treatments.
Article
Chemistry, Physical
Alessandro Longo, Francesco Giannici, Maria Pia Casaletto, Mauro Rovezzi, Christoph J. Sahle, Pieter Glatzel, Yves Joly, Antonino Martorana
Summary: HERFD-XANES was used to study the modifications of gold 5d orbital during the activation of molecular oxygen, revealing the dynamism of gold electronic configuration during the reaction process.
Article
Multidisciplinary Sciences
Caroline Bissardon, Marie-Pierre Isaure, Emmanuel Lesuisse, Mauro Rovezzi, Eric Lahera, Olivier Proux, Sylvain Bohic
Summary: The study of metals in biological systems using X-ray absorption spectroscopy (XAS) is of great interest. Sample preparation, especially for biological samples, is a critical and complex procedure. This paper proposes a cellular preparation protocol based on cryo-preserved samples, which allows for the analysis of biological samples in their near-native hydrated state to preserve the chemical integrity.
JOVE-JOURNAL OF VISUALIZED EXPERIMENTS
(2022)
Article
Chemistry, Multidisciplinary
Alain Manceau, Alexandre Simionovici, Nathaniel Findling, Pieter Glatzel, Blanka Detlefs, Anna Wegorzewski, Kira Mizell, James R. Hein, Andrea Koschinsky
Summary: Our study reveals the mechanism of Tl partitioning in FeMn deposits under different environmental conditions by investigating the oxidation state and chemical form of Tl in FeMn crusts and nodules from the global oceans, and finds that Tl has a high affinity with vernadite regardless of its oxidation state.
ACS EARTH AND SPACE CHEMISTRY
(2022)
Article
Chemistry, Physical
Ricardo Sgarbi, Kavita Kumar, Viktoriia A. Saveleva, Laetitia Dubau, Raphael Chattot, Vincent Martin, Michel Mermoux, Pierre Bordet, Pieter Glatzel, Edson A. Ticianelli, Frederic Jaouen, Frederic Maillard
Summary: Fe-N-C catalysts show limited stability in acidic medium and may benefit from protective measures. Additionally, a possible synergy between Fe oxide nanoparticles and Fe-NxCy single-atom sites may contribute to higher apparent durability.
APPLIED CATALYSIS B-ENVIRONMENTAL
(2022)
Article
Chemistry, Physical
Kerstin Wissel, Fabio Bernardini, Heesu Oh, Sami Vasala, Roland Schoch, Bjoern Blaschkowski, Pieter Glatzel, Matthias Bauer, Oliver Clemens, Andres Cano
Summary: Understanding high-temperature unconventional superconductivity has always been a long-standing problem, with cuprates as central reference materials. The recent discovery of superconductivity in analogous nickelate thin films marks a fundamental breakthrough, calling for the search of additional materials in this class. In this study, a new single-layer T' Pr2NiO3F compound was synthesized and compared with the previously synthesized T' nickelate La2NiO3F. The electronic properties of the R2NiO3F series (R = La-Lu) were analyzed using first-principles calculations. The mixed anion systems were found to have a high degree of stability, and their composition could be finely tuned through synthesis. Furthermore, these unprecedented square-planar nickelates show great promise as potential superconductors due to their exceptional electronic structure.
CHEMISTRY OF MATERIALS
(2022)
Article
Chemistry, Multidisciplinary
Alain Manceau, Sophie A. L. Paul, Alexandre Simionovici, Valerie Magnin, Melanie Balvay, Nathaniel Findling, Mauro Rovezzi, Samuel Muller, Dieter Garbe-Schonberg, Andrea Koschinsky
Summary: Detailed studies on rare earth elements and yttrium (REY)-containing bioapatites in ocean-floor sediments have been conducted using laser ablation inductively coupled plasma diffraction analysis and Ce L3-edge high energy-resolution X-ray absorption near edge structure (HR-XANES) spectroscopy, providing valuable insights into their geochemical properties and mineralogical variations.
ACS EARTH AND SPACE CHEMISTRY
(2022)
Article
Chemistry, Physical
Viktoriia A. Saveleva, Kavita Kumar, Pascal Theis, Nicole Segura Salas, Ulrike I. Kramm, Frederic Jaouen, Frederic Maillard, Pieter Glatzel
Summary: This study investigates the structural composition of Fe-N-C materials for the oxygen reduction reaction in proton-exchange membrane fuel cells, before and after catalyst layer preparation, using X-ray absorption and emission spectroscopies. The results reveal the significant impact of the preparation step on the electronic structure and local coordination of Fe, emphasizing the importance of determining the Fe-N-C catalyst structure in the prepared electrode for further studies of the structure-activity-stability correlations.
ACS APPLIED ENERGY MATERIALS
(2023)
Article
Chemistry, Analytical
Blanka Detlefs, Serena Graziano, Pieter Glatzel
Summary: We present a protocol for efficiently detecting the chemical state of an element using X-ray emission (fluorescence) spectroscopy with a Bragg optics spectrometer. The intensity ratio at two specific X-ray emission energies, which is largely free from experimental artifacts, can accurately identify the chemical state. Differences in chemical states in spatially inhomogeneous or temporally evolving samples can be detected with low numbers of photon events, reducing data acquisition time by two orders of magnitude compared to recording a full spectrum.
ANALYTICAL CHEMISTRY
(2023)
Article
Chemistry, Physical
K. Teixeira Santos, K. Kumar, L. Dubau, H. Ge, S. Berthon-Fabry, C. S. A. Vasconcellos, F. H. B. Lima, T. Asset, P. Atanassov, V. A. Saveleva, P. Glatzel, X. Li, F. Jaouen, F. Maillard
Summary: Tremendous progress has been made in improving the oxygen reduction reaction (ORR) activity of iron nitrogen carbon (Fe-N-C) catalysts, which have the potential to replace platinum-group metals in proton exchange membrane fuel cells cathode. However, the degradation mechanisms and practical durability of these catalysts remain major challenges. This study reports on the spontaneous aerobic degradation phenomenon of Fe-N-C materials under atmospheric conditions, which leads to a decrease in their electrocatalytic activity towards the ORR.
JOURNAL OF POWER SOURCES
(2023)
Article
Chemistry, Inorganic & Nuclear
Claire Le Gall, Vincent Klosek, Fabienne Audubert, Jacques Lechelle, Doris Drouan, Jean-Christophe Richaud, Yves Pontillon, Myrtille O. J. Y. Hunault, Pier Lorenzo Solari, Mauro Rovezzi, Jean-Louis Hazemann
Summary: To understand the behavior of fission products during a Nuclear Severe Accident, simulated high burnup UO2 fuels (SIMFUEL) were thermally treated under conditions representative of a Pressurized Water Reactor severe accident. The samples were characterized before and after heat treatments using SEM-EDX and XAS. Results showed that at around 1000°C, Mo oxidizes into MoO2 and interacts with the perovskite phase containing Ba to form BaMoO4.
JOURNAL OF SOLID STATE CHEMISTRY
(2023)