Understanding direct metal-metal bonding between actinide atoms has been an elusive goal in chemistry for years. We report for the first time the anion photoelectron spectrum of U. The threshold of the lowest electron binding energy (EBE) spectral band occurs at 1.0 eV, which corresponds to the electron affinity (EA) of U, whereas the vertical detachment energy of U is found at EBE ∼ 1.2 eV. Electronic structure calculations on U and U were carried out with state-of-the-art theoretical methods. The computed values of EA(U) and EA(U) and the difference between the computed dissociation energies of U and U are found to be internally consistent and consistent with experiment. Analysis of the bonds in U and U shows that while U has a formal quintuple bond, U has a quadruple bond, even if the effective bond orders differ only by 0.5 unit instead of one unit. The resulting experimental-computational synergy elucidates the nature of metal-metal bonding in U and U.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/jacs.1c06417 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Silver-purine MOFs for high-performance multi-terminal neuromorphic memory.
Mater Horiz
January 2025
School of Chemical Sciences, National Institute of Science Education and Research (NISER), An OCC of HBNI, Bhubaneswar, 752050, Odisha, India.
Neuromorphic and fully analog in-memory computations are promising for handling vast amounts of data with minimal energy consumption. We have synthesized and studied a series of homo-bimetallic silver purine MOFs (1D and 2D) having direct metal-metal bonding. The N7-derivatized purine ligands are designed to form bi-metallic complexes under ambient conditions, extending to a 1D or 2D metal-organic framework.
View Article and Find Full Text PDFHeterobimetallic contacts in statistical co-crystals of homoleptic coordination compounds with ligand-encoded H⋯F bonds: structure, photophysics and mechano-responsive properties.
Chem Commun (Camb)
December 2024
Institut für Anorganische und Analytische Chemie, Universität Münster, Corrensstraße 28/30, 48149 Münster, Germany.
In this work, the structural and photophysical characterization of statistical co-crystals based on two homoleptic Pt(II) and Pd(II) complexes as well as their mechano-responsive properties are reported. Ligand-dominated H⋯F bonds, which reinforce metal-metal interactions in the crystalline state, support emission from MMLCT states. All co-crystals show a distinct red-shift upon grinding, showcasing their inherent mechano-responsive characteristics stemming from (hetero-)bimetallic contacts.
View Article and Find Full Text PDFAssembling Di- and Polynuclear Cu(I) Complexes with Rigid Thioxanthone-Based Ligands: Structures, Reactivity, and Photoluminescence.
Inorg Chem
December 2024
Institute of Chemistry, Hebrew University of Jerusalem, Jerusalem 9190401, Israel.
Thioxanthone (TX) molecules and their derivatives are well-known photoactive compounds. Yet, there exist only a handful of luminescent systems combining TX with transition metals. Recently, we reported a TX-based PSP pincer ligand () that appears as a promising platform for filling this niche.
View Article and Find Full Text PDFFluoride Clusterfullerenes: Tuning Metal-Metal Bonding and Magnetic Properties via Single Fluorine Atom Doping.
J Am Chem Soc
December 2024
College of Chemistry, Chemical Engineering and Materials Science, and State Key Laboratory of Radiation Medicine and Protection, Soochow University, Suzhou, Jiangsu 215123, P. R. China.
Article Synopsis
- Endohedral fullerenes are molecules that can encapsulate metal clusters, and this study introduces a new type called fluoride clusterfullerenes (FCFs).
- The researchers successfully synthesized FCFs using various actinides, rare earth metals, and alkaline earth metals without needing extra modifications, revealing that adding a fluorine atom alters the metal-metal bonding significantly.
- Their findings indicate that compounds like ThF@(7)-C and CaScF@(6)-C exhibit unique bonding interactions and promising magnetic properties, showcasing the potential of FCFs in future applications.
The diradicaloid electronic structure of dialumenes: a benchmark study at the Full-CI limit.
Phys Chem Chem Phys
December 2024
Department of Chemistry, Maynooth University, Maynooth, Co. Kildare, Ireland.
Article Synopsis
- Multiply-bonded main group compounds from groups 13-15, like dialumenes, are gaining attention for their unique metal-metal bonding and potential applications in catalysis and small molecule activation.
- The study focuses on the simplest dialumene, AlH, analyzing its electronic structure and bond dissociation energy using advanced quantum chemistry methods to set a reference for other computational techniques.
- The results show that while single-reference coupled cluster theory can effectively capture the diradical character of dialumene, density functional methods struggle with accuracy, though some approaches like non-hybrid TPSS yield better results than high-percentage hybrids.
Want AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!