Article
Chemistry, Inorganic & Nuclear
Omar J. Garcia, Laure Vendier, Michel Etienne, Steven Gwaltney, Abigail Ressler, Miguel-Angel Munoz-Hernandez
Summary: In this study, the transfer of alkyl bis- and tris(pyrazolyl)aluminates to an electron-rich organotransition metal center was reported, resulting in the formation of 16-electron heterobimetallic rhodium complexes. These complexes exhibited enhanced catalytic activity in the polymerization of phenylacetylene compared to analogous rhodium poly(pyrazolyl)borates.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Daniel Pividori, Matthias E. Miehlich, Benedikt Kestel, Frank W. Heinemann, Andreas Scheurer, Michael Patzschke, Karsten Meyer
Summary: The study reports the synthesis of a novel sulfur-based ligand and its coordination chemistry with low-valent uranium, as well as the characterization of the resulting compound in terms of molecular structure and magnetic behavior. Comparative analysis with previously reported ligands sheds light on the electronic structure changes.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Johannes Kretsch, Anne Kreyenschmidt, Timo Schillmoeller, Christian Sindlinger, Regine Herbst-Irmer, Dietmar Stalke
Summary: In this study, neutral monovalent group 13 complexes were synthesized using a bulky bis(4-benzhydryl-benzoxazyl-2-yl)methane ligand, with compounds including Tl, In, and Ga. Additionally, a potential precursor for an aluminum(I) congener was successfully synthesized through two alternative synthetic routes. All main products were thoroughly characterized by various analytical techniques, such as nuclear magnetic resonance spectroscopy and single-crystal X-ray structure determination.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Andrey V. Pichugov, Andrey V. Rumyantsev, Nikolai S. Bushkov, Anton A. Zhizhin, Dmitry Yu. Aleshin, Valeria N. Talanova, Rina U. Takazova, David Trummer, Deni Mance, Pavel A. Zhizhko, Dmitry N. Zarubin
Summary: Surface Organometallic Chemistry (SOMC) combines surface science techniques and molecular organometallic chemistry to selectively prepare unusual or highly reactive species on inorganic supports. In this report, we utilize SOMC protocols to prepare well-defined silica-supported Zr imido complexes and compare their catalytic activity with highly active supported Ti systems. We also investigate the stoichiometric reactivity of Zr imides and discuss the correlation between electronic structure and catalytic performance of silica-supported species.
INORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Inorganic & Nuclear
Brandon T. Watson, Mukundam Vanga, Anurag Noonikara-Poyil, Alvaro Munoz-Castro, H. V. Rasika Dias
Summary: Bis-and tris-pyridyl borate ligands with pyridyl donor arms, a methylated boron cap, and a fluorine-lined coordination pocket have been synthesized and used in coinage metal chemistry. These ligands allowed for the isolation of group 11 metal-ethylene complexes, with gold complexes showing the largest coordination-induced upfield shifts of the ethylene 13C resonance. Solid-state structures of these complexes revealed the rare K2 coordination mode instead of the typical K3 coordination mode. Computational analyses indicated the favored K2 coordination mode and the strong interaction between gold(I) and ethylene.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Samuel Francis, Craig R. Rice, Paul A. Scattergood, Paul I. P. Elliott
Summary: The tris(1,2,3-triazol-4-yl)methane framework is a highly versatile architecture for ligand design, but its coordination chemistry is still underexplored. This study reports the synthesis and characterization of three homoleptic complexes [M(ttzm)(2)](PF6)(2) (ttzm = tris(1-benzyl-1,2,3-triazol-4-yl)-p-anisolylmethane; M = Fe (Fe), Ru (Ru), Os (Os)). These complexes exhibit unique properties such as distorted structures, reversible redox processes, and UV-visible absorption. In particular, Os shows emissive properties at low temperatures.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Amy N. Price, Ankur K. Gupta, Wibe A. de Jong, Polly L. Arnold
Summary: The chemistry of the tris-carbene anion phenyltris(3-alkyl-imidazoline-2-yliden-1-yl)borate, [C3(Me)](-) ligand, for f-block metal cations was investigated. Neutral, molecular complexes were formed for cerium(iii), while a separated ion pair was formed for ytterbium(iii). Computational analyses demonstrated the stronger s donation and greater covalency in the metal-carbon bonds of the [C3(Me)](-) complexes compared to the Tp(Me,Me) complexes. DFT calculations confirmed the crucial role of THF solvent in accurately reproducing the observed molecular and ion-pair geometries for the Ce and Yb complexes.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Yuyuan Xiao, Rong Sun, Jiefeng Liang, Yuhui Fang, Zheng Liu, Shangda Jiang, Bingwu Wang, Song Gao, Wenliang Huang
Summary: The synthesized rare earth metal complexes exhibit complex electronic structures and magnetic behaviors. The structural and magnetic data are consistent with density functional theory calculations, revealing the antiferromagnetic coupling between the radical anions.
INORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Inorganic & Nuclear
Si-Hai Wu, Rong Yang, Bin Sun, Jian-Hong Tang, Zhong-Liang Gong, Junjie Ma, Lianhui Wang, Jieqing Liu, Dian-Xue Ma, Jiang-Yang Shao, Yu-Wu Zhong
Summary: Three tris-heteroleptic mononuclear Ru(II) complexes with dual fluorescence and phosphorescence were designed and used as ratiometric light-response probes for DNA, where two of the complexes exhibited stronger preference for calf thymus DNA. The interactions of these complexes with different DNAs were investigated by various methods, including spectroscopy and molecular modeling, providing valuable insights for potential applications in DNA sensing.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Applied
Dmitry Erzunov, Anastasia Rassolova, Anna Botnar, Svetlana Tonkova, Roman Rumyantsev, Vladimir Maizlish, Viktor Aleksandriskii, Arthur Vashurin
Summary: Isomeric 4-[(methoxy)phenoxy]phthadinitriles with high thermal stability were obtained and characterized. X-ray diffraction analysis revealed that intermolecular interactions, such as π-stacking and three-center intermolecular bonds, contributed to their packing. Novel metal complexes with tetrakis-4-[4-(o-/m-/p-methoxy)phenoxy]phthalocyanine ligands were synthesized and their structure, spectroscopic properties, and luminescent properties were determined. The position of the methoxy-group affected the fluorescence quantum yields of the compounds but had almost no effect on their fluorescence lifetimes.
Article
Chemistry, Inorganic & Nuclear
Wintana Tzegai, Michaela Reil, Nicolai Burzlaff
Summary: This study describes a ligand based on bis(4-carboxylpyrazol-1-yl)acetic acid and its corresponding carbonyl metal complexes. The solubility of the ligand in solution differs for carboxyl groups, and the peripheral carboxyl groups are not involved in metal coordination.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Physical
Wiebke Wackerow, Zeynabou Thiam, Edy Abou-Hamad, Walid Al Maksoud, Mohamed N. Hedhili, Jean-Marie Basset
Summary: The article discusses the unique catalytic properties of tungsten-hydrides supported on oxide supports, suggesting that supported tungsten-hydride complexes coexist on the support as bis-hydride and tris-hydride species.
JOURNAL OF PHYSICAL CHEMISTRY C
(2021)
Article
Chemistry, Inorganic & Nuclear
Stephen Sproules
Summary: Spectroscopic and computational examination reveals a Class III mixed-valent ground state for the neutral tris-dioxolene complex [V(dbcat)(3)]. The radical is stabilized by delocalization across the ligands mediated by the V(v) center's energy matched d orbital manifold. This electronic structure differs from the tris-dithiolene and tris-diimine analogues with V(iv) and V(ii) ions, respectively.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Angela Vivancos, Delia Bautista, Pablo Gonzalez-Herrero
Summary: This study reports the synthesis, structure, photophysical properties, and electrochemistry of the first series of Pt(IV) tris-chelates bearing cyclometalated aryl-NHC ligands. The complexes exhibit significant photostability, long-lived phosphorescence, and potential application for Pt(IV) emitters with tunable properties.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Alvaro Garcia-Romero, Daniel Miguel, Dominic S. Wright, Celedonio M. Alvarez, Raul Garcia-Rodriguez
Summary: This paper explores the use of main group elements in supramolecular chemistry, specifically in supramolecular porphyrin-based capsules. By studying the periodic trends in the p-block, the authors demonstrate how size and structural control of the capsules can be achieved. The interaction between heavier Group 15 tris(3-pyridyl) linkers and metallo-porphyrins has been investigated, revealing the influence of bond length and oxidation state on the dimensions and reactivity of the capsules.
Article
Materials Science, Multidisciplinary
Jia-Li Chen, Nikolas Kaltsoyannis
Summary: Understanding actinide mixed oxides is crucial for the development of nuclear fuel and the storage of spent fuel. This study provides systematic simulations of AnO(2) and U-An MOX using density functional theory, focusing on spin density and density of states. Conclusions are drawn regarding oxidation states and transition regions between different systems.
JOURNAL OF NUCLEAR MATERIALS
(2022)
Letter
Multidisciplinary Sciences
Josef T. Boronski, John A. Seed, David Hunger, Adam W. Woodward, Joris van Slageren, Ashley J. Wooles, Louise S. Natrajan, Nikolas Kaltsoyannis, Stephen T. Liddle
Article
Materials Science, Multidisciplinary
Lin Yang, Nikolas Kaltsoyannis
Summary: Density functional theory is used to study the diffusion properties of U atoms and noble gas fission products in uranium mononitride, revealing the influence of stoichiometric conditions on diffusion of U and differences in diffusion coefficients of Kr and Xe via different mechanisms.
JOURNAL OF NUCLEAR MATERIALS
(2022)
Article
Chemistry, Multidisciplinary
Charlotte Morrill, Aron Peter, Ilma Amalina, Emma Pye, Giacomo E. M. Crisenza, Nikolas Kaltsoyannis, David J. Procter
Summary: Reductive cyclizations of carbonyl compounds mediated by SmI2 provide a stereocontrolled approach to generate molecular complexity. While previous studies mainly focused on ketone and aldehyde substrates, this research demonstrates the successful cyclization of lactone and lactam-type substrates as well. Additionally, the study presents a novel diastereoselective radical 1,4-ester migration process mediated by SmI2, allowing the formation of stereodefined alkene hydrocarboxylation products via radical cyclization of acyclic ester groups.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Multidisciplinary Sciences
Amy N. Price, Victoria Berryman, Tatsumi Ochiai, Jacob J. Shephard, Simon Parsons, Nikolas Kaltsoyannis, Polly L. Arnold
Summary: The article explores whether low-coordinate f-block molecules become more planar or pyramidal under pressure using high-pressure crystallography, with the result being dictated by the dipole moment of the complex and the volume of the planar form.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Nicholas Greaves, Nikolas Kaltsoyannis
Summary: The geometries, electronic structures, and spin state energetics of multi-layer Matryoshka actinyl peroxide manganese nanoclusters have been studied using generalised gradient approximation and hybrid density functional theory. Strong linear correlations were found between the number of unpaired electrons and the energies of the complexes, with the highest spin states being the most stable. The compositions of molecular orbitals associated with changing spin states were studied in detail, providing insight into the relative energies of different spin states.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Multidisciplinary Sciences
Jacob J. Shephard, Victoria E. J. Berryman, Tatsumi Ochiai, Olaf Walter, Amy N. Price, Mark R. Warren, Polly L. Arnold, Nikolas Kaltsoyannis, Simon Parsons
Summary: The study shows that pressure can distort actinide-oxygen bonding, and the effects vary for different actinide elements due to their atomic size. Electronic structure calculations reveal that the increased contributions of metal 6d and 5f orbitals to the metal-oxygen bonding result in the shortening of these bonds and enhance the flexibility of MO4 cores.
NATURE COMMUNICATIONS
(2022)
Article
Nanoscience & Nanotechnology
Fanxing Xi, Farabi Bozheyev, Xiaoyu Han, Marin Rusu, Joerg Rappich, Fatwa F. Abdi, Peter Bogdanoff, Nikolas Kaltsoyannis, Sebastian Fiechter
Summary: Thiomolybdate [Mo3S13]2- nanoclusters are a promising catalyst for hydrogen evolution reaction, showcasing high activity edge sites. The clusters demonstrate low overpotential and structural stability in sulfuric acid electrolyte, as well as significantly enhanced photocurrent on WSe2.
ACS APPLIED MATERIALS & INTERFACES
(2022)
Article
Materials Science, Multidisciplinary
Lin Yang, Nikolas Kaltsoyannis
Summary: This work investigates the properties of mixed nitrides U0.75Pu0.25N and U0.5Pu0.5N, as well as the incorporation and migration behavior of fission gas Xe. The results show that the disordered structures have closer lattice parameters to experimental values and lower energy states for Pu f orbitals than U f orbitals. Furthermore, the vacancy formation energy and Xe incorporation energy depend on the chemical environment.
JOURNAL OF NUCLEAR MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Soumitra Agasti, Frederic Beltran, Emma Pye, Nikolas Kaltsoyannis, Giacomo E. M. Crisenza, David J. J. Procter
Summary: A general synthetic route to substituted bicyclo[2.1.1]hexanes (BCHs) has been developed through intermolecular coupling between olefins and bicyclo[1.1.0]butyl (BCB) ketones. The SmI2-catalysed process can be applied to a wide range of electron-deficient alkenes and substituted BCB ketones, with low loadings of SmI2. The resulting BCH ketones have been shown to be versatile synthetic intermediates and can be used for selective downstream manipulation and the expedient synthesis of a saturated hydrocarbon analogue of the broad-spectrum antimicrobial, phthalylsulfathiazole.
Article
Chemistry, Inorganic & Nuclear
Bono van IJzendoorn, Jessica B. M. Whittingham, George F. S. Whitehead, Nikolas Kaltsoyannis, Meera Mehta
Summary: In this study, the boron functionalized [P7] cluster was applied in organic transformations, including dearomatized reduction of pyridines and hydroboration of imines and nitriles, leading to the synthesis of amine compounds. The catalyst exhibited high stability and could be recycled multiple times without loss in performance. The mechanism of the pyridine reduction was investigated experimentally and computationally. This work demonstrates the potential of boron functionalized phosphorus Zintl clusters as transition metal-free catalysts for nitrogen-containing substrates.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Bono van IJzendoorn, Jessica B. M. Whittingham, George F. S. Whitehead, Nikolas Kaltsoyannis, Meera Mehta
Summary: This study demonstrates that boron functionalized phosphorus Zintl cluster can serve as a catalyst for the reduction of nitrogen containing substrates. The catalyst showed high stability and could be recycled multiple times without loss in performance.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
David M. King, Benjamin E. Atkinson, Lucile Chatelain, Matthew Gregson, John A. Seed, Ashley J. Wooles, Nikolas Kaltsoyannis, Stephen T. Liddle
Summary: In this study, a unique diuranium(IV) dinitride compound [{U-IV(mu-NLi2)(Tren(TIPS))}(2)] was synthesized by treating [U-IV(N3)(Tren(TIPS))] with Li. The reduction sequence 1 -> 4 -> 2 -> 3 was proposed based on the obtained products. It was found that lithium plays a crucial role in stabilizing the charge accumulation in the nitride. The magnetic data analysis of the synthesized compounds 2 and 5 suggests a doubly degenerate ground state with strong crystal field effects dominating over spin-orbit coupling.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Sophie Cooper, Nikolas Kaltsoyannis
Summary: By using computational methods to study actinide chlorides, it is found that the dichlorides of later actinide elements have fewer covalent bonds compared to their trichloride counterparts, and the degree of energy match between the actinide 5f orbitals and the ligand 3p orbitals determines the change in covalency.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Physical
William D. Neilson, Helen Steele, Nikolas Kaltsoyannis, Samuel T. Murphy
Summary: This study investigates the incorporation of helium in plutonium dioxide using density functional theory and a point defect model. The simulations suggest that helium is mainly accommodated as an interstitial in the lattice, and its preference for oxygen vacancy sites increases with material ageing.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Multidisciplinary
Alexander M. Prophet, Kritanjan Polley, Gary J. Van Berkel, David T. Limmer, Kevin R. Wilson
Summary: The oxidation kinetics of iodide by ozone at the air-water interface is studied in single microdroplets. Molecular simulations and kinetic modeling are used to understand the underlying multiphase mechanism.
Article
Chemistry, Multidisciplinary
Rong Zhang, Jiajing Lan, Fei Wang, Shumei Chen, Jian Zhang
Summary: By utilizing 1,1'-ferrocene dicarboxylic acid as a chelating and surface protection ligand, we have synthesized multi-nuclear indium oxide clusters with varying nuclear sizes, including heptanuclear and thirteen-nuclear clusters. These clusters possess labile coordination sites, allowing for structural modification and self-assembly, resulting in the formation of various cluster structures.
Article
Chemistry, Multidisciplinary
Hui Wang, Hui Liu, Mingsen Wang, Jiaheng Hou, Yongjun Li, Yuancheng Wang, Yingjie Zhao
Summary: Two supramolecular complexes were prepared using CBs and M1, and their single-crystal structures were analyzed by SCXRD. The unexpected 1:2 self-assembly structure between M1 and CB[8] was discovered for the first time. These complexes exhibit unique photophysical properties and provide valuable information about the structure and photophysical properties of supramolecular complexes.
Article
Chemistry, Multidisciplinary
Chang-Hee Lee, Sookil Park, Sanggil Kim, Ji Young Hyun, Hyun Soo Lee, Injae Shin
Summary: The epidermal growth factor receptor (EGFR) is a cell-surface glycoprotein involved in cell proliferation and tumor development. This study used a fluorescently labeled EGFR to investigate its time-dependent endocytosis in live cells and found that appended glycans affect EGFR internalization. Additionally, the study detected sialic acid residues attached to EGFR on the live cell surface using FRET-based imaging. This research provides valuable insights into the cellular functions of EGFR.
Article
Chemistry, Multidisciplinary
Subhankar Sahu, Lokesh Kumar, Sumita Das, Dipti Gupta, Ruchi Anand
Summary: This study proposes a strategy that combines organic electronics with biosensor scaffolds to create a compact device for monitoring environmental aromatic pollution. By coupling biosensing protein MopR with an organic electrochemical transistor (OECT), a sensor module capable of efficient detection of phenol was designed. Exclusive phenol detection with minimal loss of sensitivity could be achieved in complex pollutant mixtures and real environmental samples.
Review
Chemistry, Multidisciplinary
Changseok Lee, Hyung-Joon Kang, Sungwoo Hong
Summary: The formation of C-N bonds through hydroamination reactions catalyzed by nickel hydrides has been a topic of recent interest. This approach offers a way to efficiently transform a variety of alkene and alkyne substrates into compounds enriched with C-N bonds. The review provides a concise overview of the underlying reaction mechanisms and aims to stimulate further progress in NiH-catalytic techniques and catalyst design.
Article
Chemistry, Multidisciplinary
Yueci Wu, Lu-Lu Sun, Hai-Hao Han, Xiao-Peng He, Weiguo Cao, Tony D. James
Summary: Drug-induced liver injury (DILI) is a common cause of acute liver failure in the USA and Europe, but most cases can be recovered or prevented by discontinuing the offending drug. Recent research has found that peroxynitrite (ONOO-) can be used as a potential indicator for early diagnosis of DILI, and there is an urgent need to establish a method to detect and track peroxynitrite in DILI cases. In this study, a FRET-based nano fluorescent probe CD-N-I was developed, which showed high selectivity and sensitivity in detecting peroxynitrite. The probe successfully detected exogenous peroxynitrite in live cells and endogenous peroxynitrite in APAP-induced liver injury of HepG2 cells.
Article
Chemistry, Multidisciplinary
Dmitry L. Lipilin, Mikhail O. Zubkov, Mikhail D. Kosobokov, Alexander D. Dilman
Summary: This article describes a direct photocatalytic method for the thiolation of unprotected acids, which was previously challenging. By using a thionocarbonate reagent with an N-O bond, the efficient conversion of carboxylic acids to thiols is achieved.
Article
Chemistry, Multidisciplinary
Jason Malenfant, Lucille Kuster, Yohann Gagne, Kouassi Signo, Maxime Denis, Sylvain Canesi, Mathieu Frenette
Summary: Raman microscopy can reveal compound-specific vibrational fingerprints without sample preparation. The combination of efficient theoretical calculations and a user-friendly software can accurately predict peak positions and provide match scores to assist with structure determination.
Article
Chemistry, Multidisciplinary
Jayoh A. Hernandez, Paul S. Micus, Sean Alec Lois Sunga, Luca Mazzei, Stefano Ciurli, Gabriele Meloni
Summary: Essential trace metals play crucial roles in the survival and virulence of bacterial pathogens. Helicobacter pylori requires nickel for colonization and persistence in the stomach, and NixA is an essential nickel transporter in this process. This study characterizes the selectivity and electrogenic nature of NixA-mediated nickel transport.
Article
Chemistry, Multidisciplinary
Tarali Devi, Kuheli Dutta, Jennifer Deutscher, Stefan Mebs, Uwe Kuhlmann, Michael Haumann, Beatrice Cula, Holger Dau, Peter Hildebrandt, Kallol Ray
Summary: This study emphasizes the importance of subtle electronic changes and secondary interactions in the stability of biologically relevant metal-dioxygen intermediates. It also shows that the role of the chloride ligand in stabilizing the Fe-III-(OOBu)-Bu-t moiety can extend to other anions, including the thiolate ligand.
Article
Chemistry, Multidisciplinary
Jacqueline R. Santhouse, Jeremy M. G. Leung, Lillian T. Chong, W. Seth Horne
Summary: By studying the folding kinetics and mechanism of the BdpA sequence, researchers found that altering the backbone connectivity can affect protein folding. This suggests that protein mimetic chains have a significant degree of plasticity in transitioning between unfolded and folded states.
Article
Chemistry, Multidisciplinary
Divanshu Gupta, Ralf Einholz, Holger F. Bettinger
Summary: This study presents the first direct spectroscopic evidence of a cyclic seven-membered iminoborane. Compared to linear amino-iminoboranes, this cyclic iminoborane exhibits weakened bond strength and lower Lewis acidity value. The study suggests that the reduced ring strain of cyclic iminoborane prevents nitrogen fixation but allows facile (2 + 2) cycloaddition reaction with C2H4.
Article
Chemistry, Multidisciplinary
Renny Mathew, Aniruddha Mazumder, Praveen Kumar, Julie Matula, Sharmarke Mohamed, Petr Brazda, Mahesh Hariharan, Brijith Thomas
Summary: This study reveals the packing arrangement of partially disordered nitro-perylenediimide (NO2-PDI) using a synergistic approach that combines 3D ED, ssNMR, and DFT techniques. By overcoming these challenges, this methodology opens up new avenues for material characterization, driving exciting advancements in the field.
