Article
Chemistry, Inorganic & Nuclear
James D. Nobbs, Dillon Wei Peng Tay, Yoon Hui Yeap, Yong Lun Tiong, Suming Ye, Srinivasulu Aitipamula, Cun Wang, Choon Boon Cheong, Martin van Meurs
Summary: Dioxaphosphabicyclo[2.2.2]octanes were synthesized in a one-pot reaction and showed excellent performance and activity as ligands in catalytic reactions.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Mikaela M. Pyrch, Logan J. Augustine, James M. Williams, Sara E. Mason, Tori Z. Forbes
Summary: In this study, the vibrational frequencies of different neptunyl-neptunyl subunits (dimeric, trimeric, tetrameric) were determined using computational and experimental approaches. The results showed that the additional signals in the vibrational spectra were attributed to the interactions between trimeric and tetrameric actinyl subunits. The combination of computational studies and vibrational analysis allowed for the assignment of spectral features to different polymerized subunits in different anionic systems.
DALTON TRANSACTIONS
(2022)
Article
Engineering, Environmental
Alandra M. Lopez, Arden Wells, Scott Fendorf
Summary: This study combines machine learning and geochemical modeling to investigate the controls on regional groundwater uranium contamination in the Central Valley, California, identifying key predictors of groundwater uranium concentrations. The study shows that groundwater uranium exceedances of drinking water standards are dependent on the formation of uranyl-calcium-carbonato species, which are in part created by infiltration through the vadose zone, highlighting the critical dependence of groundwater quality on recharge conditions.
ENVIRONMENTAL SCIENCE & TECHNOLOGY
(2021)
Article
Chemistry, Inorganic & Nuclear
Danielle E. Smith, William Levason, James Powell, Gillian Reid
Summary: Various oxotrichloromolybdenum(v) complexes with group 16 donor ligands have been synthesized and characterized, including a novel telluroether compound with molybdenum in a positive oxidation state. The crystal structures of several complexes were analyzed, providing clarification for conflicting literature reports.
DALTON TRANSACTIONS
(2021)
Article
Astronomy & Astrophysics
J. L. Bishop, S. J. King, M. D. Lane, A. J. Brown, B. Lafuente, T. Hiroi, R. Roberts, G. A. Swayze, J-F Lin, M. Sanchez Roman
Summary: The spectral properties of carbonates and nitrates are characterized by specific vibrational bands and absorption features, allowing for their identification on planetary surfaces. Variations in the vibrational absorptions of these minerals are influenced by mineral structure and cation size, resulting in distinct spectral features. Understanding these spectral properties is crucial for remote mapping of carbonate and nitrate chemistry on planetary bodies.
EARTH AND SPACE SCIENCE
(2021)
Article
Chemistry, Inorganic & Nuclear
Hanna Oher, Geoffroy Ferru, Laurent Couston, Laurence Berthon, Dominique Guillaumont, Florent Real, Thomas Vercouter, Valerie Vallet
Summary: Uranyl binitrate complexes are of particular interest in the nuclear industry, with the modified PUREX extraction process designed to extract U(VI) in a specific form. The DEHiBA ligands can coordinate uranyl in either trans- or cis-position with respect to the nitrate ligands, and these conformers may coexist in solution. The study aims to determine if these conformers can be discriminated by their spectroscopic properties through modeling and experimental verification.
INORGANIC CHEMISTRY
(2022)
Article
Radiology, Nuclear Medicine & Medical Imaging
Andrea Delli Pizzi, Domenico Mastrodicasa, Michele Marchioni, Giulia Primiceri, Francesca Di Fabio, Roberta Cianci, Barbara Seccia, Barbara Sessa, Erica Mincuzzi, Martina Romanelli, Pietro Castellan, Roberto Castellucci, Antonella Colasante, Luigi Schips, Raffaella Basilico, Massimo Caulo
Summary: The study concludes that a contrast-free biparametric MRI protocol consisting of T2W and DWI can serve as a reliable alternative to the standard multiparametric MRI for assessing muscle-invasive bladder cancer. The experience of different readers did not significantly affect the diagnostic performance, with a sensitivity of 100% and specificity ranging between 79.31% and 89.66%.
EUROPEAN RADIOLOGY
(2021)
Article
Chemistry, Inorganic & Nuclear
Dumitru-Claudiu Sergentu, Frederic Gendron, Eric D. Walter, Sejun Park, Cigdem Capan, R. Gian Surbella, Chuck Z. Soderquist, Gabriel B. Hall, Sergey I. Sinkov, Jochen Autschbach, Herman Cho
Summary: In this study, electric field gradient tensors in the equatorial plane of the UO22+ ion were measured and computed using NMR, NQR, and relativistic Kohn-Sham methods. The results suggest that the field gradient principal axes are sensitive to the ligand's electron donation and the environment model.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Yang-Yun Chu, Andres Garcia Alejo, Sergey L. Bud'ko, Kasuni Boteju, Smita Patnaik, Arkady Ellern, Marilu Perez Garcia, Aaron D. Sadow
Summary: The magnetic properties of 4f organometallic compounds stabilized by secondary Ln-H-Si and benzylic interactions were investigated. The compounds without a benzyl group have a larger ligand field splitting energy manifold. Doping DyR3 into LaR3 results in the crystal structure of the latter compound, and the resulting material shows hysteresis in magnetic measurements.
INORGANIC CHEMISTRY
(2023)
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)
Review
Radiology, Nuclear Medicine & Medical Imaging
Valeria Panebianco, Martina Pecoraro, Francesco Del Giudice, Mitsuru Takeuchi, Valdair F. Muglia, Emanuele Messina, Stefano Cipollari, Gianluca Giannarini, Carlo Catalano, Yoshifumi Narumi
Summary: This article reviews the current applications and future perspectives of the Vesical Imaging Reporting and Data System (VI-RADS) in bladder cancer (BCa). It discusses the role of MRI in BCa staging and treatment monitoring, as well as the clinical implications and future applications of the scoring system.
JOURNAL OF MAGNETIC RESONANCE IMAGING
(2022)
Article
Radiology, Nuclear Medicine & Medical Imaging
Maha Ibrahim Metwally, Nesma Adel Zeed, Enas Mahmoud Hamed, Al Shaimaa Fathi Elshetry, Rabab Mahmoud Elfwakhry, Ahmed M. Alaa Eldin, Ahmed Sakr, Sameh Abdelaziz Aly, Walid Mosallam, Yara Mohammed Ahmad Ziada, Rawda Balata, Ola A. Harb, Mohammad Abd Alkhalik Basha
Summary: VI-RADS showed high diagnostic validity and reliability for predicting muscle invasion by BCa, especially VI-RADS 4 and 5. However, VI-RADS 2 and 3 require further modifications to enhance their diagnostic validity. VI-RADS is highly encouraged to be used in daily practice.
EUROPEAN RADIOLOGY
(2021)
Article
Materials Science, Multidisciplinary
Benedikt Tissot, Guido Burkard
Summary: The study provides a theoretical framework for the interaction between transition metal defects in silicon carbide and nuclear spin, with potential applications for nuclear spin manipulation and long-lived nuclear-spin based quantum memories.
Article
Biochemistry & Molecular Biology
Marta Orts-Arroyo, Amadeo Ten-Esteve, Sonia Gines-Cardenas, Isabel Castro, Luis Marti-Bonmati, Jose Martinez-Lillo
Summary: The synthesized gadolinium(III) complex with high relaxivity values is considered a suitable candidate for contrast-enhanced magnetic resonance imaging, providing higher resolution and better functional images.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2021)
Article
Chemistry, Multidisciplinary
Luciano Barluzzi, Fang-Che Hsueh, Rosario Scopelliti, Benjamin E. Atkinson, Nikolas Kaltsoyannis, Marinella Mazzanti
Summary: This study reports the synthesis of the first nitride bridged uranium complexes containing U(vi) and provides a unique comparison of reactivity and bonding in U(vi)/U(vi), U(vi)/U(v) and U(v)/U(v) systems. The three complexes show very different stability and reactivity, with significant differences in the U-N bonding observed. Computational studies reveal different bonding schemes for the complexes, with delocalised or asymmetric bonds across the U-N-U structure.
Article
Chemistry, Physical
Alberto Fernandez-Alarcon, Jochen Autschbach
Summary: This paper presents a conceptual review of a frequently used localized molecular orbital (LMO) analysis method for interpreting NMR parameters in compounds containing elements from across the periodic table. An example focusing on N-15 shielding in a heavy metal complex is presented.
Article
Chemistry, Multidisciplinary
Etienne S. Gauthier, Laura Abella, Elsa Caytan, Thierry Roisnel, Nicolas Vanthuyne, Ludovic Favereau, Monika Srebro-Hooper, J. A. Gareth Williams, Jochen Autschbach, Jeanne Crassous
Summary: Describes the photophysical and chiroptical properties of a novel, chiral helicene-NHC-Re(I) complex with an N-(aza[6]helicenyl)-benzimidazolylidene ligand, showing its capability of emitting yellow circularly polarized luminescence. A comparative analysis with other helicene-Re(I) complexes reported to date highlights the impact of structural modifications on the emissive and absorptive properties.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Editorial Material
Chemistry, Physical
Alberto Fernandez-Alarcon, Jochen Autschbach
Summary: This article presents the phenomenon of molecules producing spectroscopic signals in NMR through their orbitals interacting with an electromagnetic field, with the front cover artwork provided by Dr. Alberto Fernandez-Alarcon.
Article
Chemistry, Physical
Jochen Autschbach, Adam Philips
Summary: A comprehensive calculation of proton NMR relaxation in water, acetonitrile, and methane is provided using ab initio and force-field-based molecular dynamics simulations. The formalism developed for the spin-rotation contribution to relaxation can be applied to any molecular symmetry and calculates the full molecular spin-rotation tensors from first-principles using Kohn-Sham DFT. The combination of dipolar contribution calculations leads to near-quantitative agreement with total measured relaxation rates.
JOURNAL OF PHYSICAL CHEMISTRY B
(2023)
Article
Chemistry, Physical
Kais Dhbaibi, Pierpaolo Morgante, Nicolas Vanthuyne, Jochen Autschbach, Ludovic Favereau, Jeanne Crassous
Summary: This study reports the experimental measurement of the photophysical and chiroptical properties of helicene-based pi-conjugated emitters with electron-accepting or donating moieties at low temperature. The samples exhibit strong circularly polarized phosphorescence with high luminescence dissymmetry factor and long lifetime for the most active molecule, the nitro compound. The theoretical investigation reveals that the emissions of singlet and triplet excited states mainly come from the helicene core with different rotatory strengths due to the absence of strong mixing between these states.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Multidisciplinary
Hongjie Jiang, Xiaojuan Yu, Min Guo, Yang-Rong Yao, Qingyu Meng, Luis Echegoyen, Jochen Autschbach, Ning Chen
Summary: Two new actinide-rare earth mixed metal carbides and nitrogen carbide cluster fullerenes, USc2C2@D5h(6)-C80 and USc2NC@D5h(6)-C80, containing U-C bonds with triple bond character, were synthesized and characterized. Crystallographic studies revealed their unique trifolate configurations, with C2/NC units vertically inserted into the plane defined by U and two Sc atoms. The U-C bonds in both molecules showed unprecedented multicenter triple-bond character, providing a deeper understanding of uranium chemistry.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Inorganic & Nuclear
Thien H. Nguyen, Xiaojuan Yu, Greggory T. Kent, Jochen Autschbach, Trevor W. Hayton
Summary: Reaction of [U(NR2)3] (R = SiMe3) with 1 equiv of bis(diisopropylamino)cyclopropenylidene (BAC) in Et2O leads to the formation of [(NR2)3U(BAC)] (1), which can be obtained in moderate yields. Thermal decomposition of 1 in C6D6 at 85 degrees C results in the formation of ring-opened U(IV) product, [(NR2)2U{N(R)-(SiMe2CH=C(NiPr2)C(NiPr2)=CH)}] (2), with low yields. The proposed mechanism suggests that 2 is formed via dissociation of BAC from 1, followed by conversion of [U(NR2)3] to [U{N(R)(SiMe2CH2)}(NR2)2] at elevated temperatures. BAC then inserts into the U-C bond of [U{N(R)(SiMe2CH2)}(NR2)2] to generate a cyclopropenyl intermediate, which undergoes ring opening and C-H activation to afford the final product, 2. It is hypothesized that the ring-opening process generates an unobserved carbene intermediate. The clean formation of 2 from a 1:1 mixture of independently prepared [U{N(R)(SiMe2CH2)}(NR2)2] and BAC provides strong support for the proposed mechanism. The formulations of both 1 and 2 were confirmed by X-ray crystallography. Theoretical calculations suggest that the hypothesized uranium carbene intermediate features strong U-C bonding.
Correction
Chemistry, Multidisciplinary
Hongjie Jiang, Xiaojuan Yu, Min Guo, Yang-Rong Yao, Qingyu Meng, Luis Echegoyen, Jochen Autschbach, Ning Chen
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Multidisciplinary Sciences
Arun Ramanathan, Jensen Kaplan, Dumitru-Claudiu Sergentu, Jacob A. Branson, Mykhaylo Ozerov, Alexander I. Kolesnikov, Stefan G. Minasian, Jochen Autschbach, John W. Freeland, Zhigang Jiang, Martin Mourigal, Henry S. La Pierre
Summary: This study reveals the failure of the traditional ionic model in tetravalent praseodymium ions, as well as the unusual participation of 4f orbitals in bonding and the anomalous hybridization of the 4f(1) configuration with ligand valence electrons. The competition between crystal-field and spin-orbit-coupling interactions alters the spin-orbital magnetism of tetravalent praseodymium, making it resemble that of high-valent actinides.
NATURE COMMUNICATIONS
(2023)
Article
Multidisciplinary Sciences
Laura C. Motta, Jochen Autschbach
Summary: In this study, the authors investigate the covalency in actinide complexes, revealing a previously overlooked fourth bonding interaction between second-row ligands and actinide. The study quantifies the energy contributions from the 6p pushing effect and inverse trans influence, providing a better understanding of actinide chemistry.
NATURE COMMUNICATIONS
(2023)
Article
Materials Science, Multidisciplinary
Patthira Sumsalee, Pierpaolo Morgante, Gregory Pieters, Jeanne Crassous, Jochen Autschbach, Ludovic Favereau
Summary: To achieve control over circularly polarized luminescence (CPL) at the molecular level without chemical modification, innovative non-conjugated chiral donor-acceptor systems were synthesized and studied. The CPL sign can be inverted by changing the solvent polarity, which is achieved through the formation of a chiral exciplex. Different solvent polarities can control the (non-) radiative deexcitation pathways, resulting in emission from locally excited or charge-transfer states with positive and negative CPL, as well as thermally activated delayed fluorescence. Theoretical calculations provide further evidence for the relationship between the emitting species and CPL. These findings offer design guidelines for switchable CPL emitters and insights into the combination of CPL and thermally activated delayed fluorescence, which are important for the development of efficient technologies based on CPL emitters.
JOURNAL OF MATERIALS CHEMISTRY C
(2023)
Article
Chemistry, Physical
Yusif Abdullayev, Nazani Karimova, Leonardo A. Schenberg, Lucas C. Ducati, Jochen Autschbach
Summary: This computational study investigates the reactions between CO2 and various substrates using a Bronsted acidic ionic liquid as a catalyst. The results show that ethylenediamine (EDA) is the most effective substrate for fixing CO2, and nonpolar solvents enhance the reaction. Modifying the ionic liquid with selenium can also be a viable option. Molecular dynamics simulations reveal that the ionic liquid ion pairs can facilitate the nucleophilic attack on CO2 through noncovalent interactions.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Adam Philips, Jochen Autschbach
Summary: A comprehensive calculation of proton NMR relaxation in water, acetonitrile, and methane was performed using ab initio and force-field-based molecular dynamics simulations. The spin-rotation (SR) contribution to relaxation was developed for use with any molecular symmetry and utilized first-principles calculations to determine the molecular SR tensors. Combination with calculations of the dipolar contribution achieved near-quantitative agreement with measured relaxation rates.
JOURNAL OF PHYSICAL CHEMISTRY B
(2023)
Correction
Chemistry, Multidisciplinary
Yi Shen, Xiaojuan Yu, Qingyu Meng, Yang-Rong Yao, Jochen Autschbach, Ning Chen
Summary: This article investigates the unexpected formation of triangular thorium carbide clusters inside C82 and C84 fullerenes.
Article
Chemistry, Physical
Giovanni Li Manni, Ignacio Fdez. Galvan, Ali Alavi, Flavia Aleotti, Francesco Aquilante, Jochen Autschbach, Davide Avagliano, Alberto Baiardi, Jie J. Bao, Stefano Battaglia, Letitia Birnoschi, Alejandro Blanco-Gonzalez, Sergey I. Bokarev, Ria Broer, Roberto Cacciari, Paul B. Calio, Rebecca K. Carlson, Rafael Carvalho Couto, Luis Cerdan, Liviu F. Chibotaru, Nicholas F. Chilton, Jonathan Richard Church, Irene Conti, Sonia Coriani, Juliana Cuellar-Zuquin, Razan E. Daoud, Nike Dattani, Piero Decleva, Coen de Graaf, Mickael G. Delcey, Luca De Vico, Werner Dobrautz, Sijia S. Dong, Rulin Feng, Nicolas Ferre, Michael Filatov(Gulak), Laura Gagliardi, Marco Garavelli, Leticia Gonzalez, Yafu Guan, Meiyuan Guo, Matthew R. Hennefarth, Matthew R. Hermes, Chad E. Hoyer, Miquel Huix-Rotllant, Vishal Kumar Jaiswal, Andy Kaiser, Danil S. Kaliakin, Marjan Khamesian, Daniel S. King, Vladislav Kochetov, Marek Krosnicki, Arpit Arun Kumaar, Ernst D. Larsson, Susi Lehtola, Marie-Bernadette Lepetit, Hans Lischka, Pablo Lopez Rios, Marcus Lundberg, Dongxia Ma, Sebastian Mai, Philipp Marquetand, Isabella C. D. Merritt, Francesco Montorsi, Maximilian Morchen, Artur Nenov, Vu Ha Anh Nguyen, Yoshio Nishimoto, Meagan S. Oakley, Massimo Olivucci, Markus Oppel, Daniele Padula, Riddhish Pandharkar, Quan Manh Phung, Felix Plasser, Gerardo Raggi, Elisa Rebolini, Markus Reiher, Ivan Rivalta, Daniel Roca-Sanjuan, Thies Romig, Arta Anushirwan Safari, Aitor Sanchez-Mansilla, Andrew M. Sand, Igor Schapiro, Thais R. Scott, Javier Segarra-Marti, Francesco Segatta, Dumitru-Claudiu Sergentu, Prachi Sharma, Ron Shepard, Yinan Shu, Jakob K. Staab, Tjerk P. Straatsma, Lasse Kragh Sorensen, Bruno Nunes Cabral Tenorio, Donald G. Truhlar, Liviu Ungur, Morgane Vacher, Valera Veryazov, Torben Arne Voss, Oskar Weser, Dihua Wu, Xuchun Yang, David Yarkony, Chen Zhou, J. Patrick Zobel, Roland Lindh
Summary: This article describes the recent developments in the open-source chemistry software environment, OpenMolcas, since spring 2020. It focuses on the new functionalities and interfaces with other packages. The article presents various topics in computational chemistry, including electronic structure theory, electronic spectroscopy simulations, molecular structure optimizations, ab initio molecular dynamics, and other new features. Overall, it highlights the capabilities of OpenMolcas in addressing chemical phenomena and processes, making it an attractive platform for advanced atomistic computer simulations.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
