The ligand field (LF) of transition metal ions is a crucial factor in realizing the mechanism of novel physical and chemical properties. However, the low-crystallinity state, including the amorphous state, precludes the clarification of the electronic structural relationship of transition metal ions using crystallographic techniques, ultraviolet and infrared optical methods, and magnetometry. Here, we demonstrate that soft X-ray 2p → 3d core-level absorption spectroscopy (-edge XAS) systematically revealed the local 3d electronic states, including in the LF, of nitrogen-coordinated transition-metal ions for low-crystallinity cyanide-bridged metal-organic frameworks (MOFs) [Ni(CN)] (MNi; = Mn, Fe, Co, Ni) and Ni[Pd(CN)] (NiPd). In NiNi and NiPd, N-coordinated Ni ions with square-planar symmetry exhibit strong orbital hybridization and ligand-to-metal charge transfer effects. In MnNi, FeNi, and CoNi, the correlation between the crystalline electric field splitting in the LF and the transition metal-nitrogen bonding length is revealed using the multiplet LF theory. Regardless of the different local symmetries, our results indicate that -edge XAS is a powerful tool for gaining element-specific knowledge about the transition-metal ion characterizing the functionality of low-crystallinity MOFs and will be the foundation for an attractive platform, such as adsorption/desorption materials.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1039/d2cp01415g | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Stabilization of Alkyltin γ-Keggin Clusters by 2, 5-Dihydroxyterephthalate Ligands.
Chem Asian J
January 2025
China Three Gorges University, Key Laboratory of Inorganic Nonmetallic Crystalline and Energy Conversion Materials, College of Materials and Chemical Engineering, China Three Gorges University, CHINA.
The Keggin clusters are one kind of the most representative molecular structures in the field of metal-oxo clusters. Although the different types of Keggin clusters with various components were reported, the research about γ-Keggin isomer remains less developed. This is ascribed to the difficulty in obtaining the stable pure γ-Keggin cluster for the structural isomerization.
View Article and Find Full Text PDFPhosphorus-Nitrogen Heterocycles Derived from Chelating N-Donor Ligands: Historical Advances, Recent Highlights, and Outlook.
Chemistry
January 2025
The University of Western Ontario, Department of Chemistry, 1151 Richmond St. N., N6A 5B7, London, CANADA.
The exploration of phosphorus-nitrogen heterocycles derived from chelating N-donor ligands is an area of research that has lagged behind the development of similar heterocycles based on other main group elements, most notably boron. The fact that phosphorus and nitrogen are both group 15 elements and that their compounds are most commonly viewed as Lewis bases likely contributes to this observation. However, through judicious ligand design and creative use of phosphorus sources that render phosphorus as Lewis acidic and/or electron poor, a variety of heterocyclic architectures are possible.
View Article and Find Full Text PDFScaled and Weighted Laplacian Matrices as Functional Descriptors for GPCR Ligands.
J Comput Chem
January 2025
Departamento de Fisicoquímica, Facultad de Química, Universidad Nacional Autónoma de México, Coyoacán, CDMX, Mexico.
The G protein-coupled receptor (GPCR) pharmacology accounts for a significant field in research, clinical studies, and therapeutics. Computer-aided drug discovery is an evolving suite of techniques and methodologies that facilitate accelerated progress in drug discovery and repositioning. However, the structure-activity relationships of molecules targeting GPCRs are highly challenging in many cases since slight structural modifications can lead to drastic changes in biological functionality.
View Article and Find Full Text PDFA rare case of a zero-field single-ion magnet in a cerium(III) pseudo-icosahedral complex.
Dalton Trans
January 2025
School of Chemistry, The University of New South Wales (UNSW), Kensington, Sydney, 2052, Australia.
The synthesis and structural characterisation of [Ln(Tp)]I (1-Ln; Ln = La, Ce, Pr, Nd) (Tp = hydrotris(3-(2'-furyl)-pyrazol-1-yl)borate) have been reported as an isomorphous series adopting pseudo-icosahedral ligand field geometries. Continuous shape measurement (CShM) analyses on the crystal field environments of 1-Ln show the smallest values yet reported for complexes employing two hexadentate ligands (-scorpionate environments), with the smallest belonging to 1-La. Single-ion magnetism for 1-Ce, 1-Pr and 1-Nd was probed with ac magnetic susceptibility studies revealing slow magnetic relaxation for 1-Nd in applied magnetic fields and in zero-applied field for 1-Ce, which is a rare observation for Ce(III)-based single-ion magnets.
View Article and Find Full Text PDFArtificial Intelligence in Computer-Aided Drug Design (CADD) Tools for the Finding of Potent Biologically Active Small Molecules: Traditional to Modern Approach.
Comb Chem High Throughput Screen
January 2025
Department of Chemistry, Integral University, Lucknow, India.
Computer-Aided Drug Design (CADD) entails designing molecules that could potentially interact with a specific biomolecular target and promising their potential binding. The stereo- arrangement and stereo-selectivity of small molecules (SMs)--based chemotherapeutic agents significantly influence their therapeutic potential and enhance their therapeutic advantages. CADD has been a well-established field for decades, but recent years have observed a significant shift toward acceptance of computational approaches in both academia and the pharmaceutical industry.
View Article and Find Full Text PDFWant 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!