The syntheses of valence tautomeric compounds with multistep transitions using new redox-active ligands are the long-term goal of the field of bistable materials. The redox-active tetraoxolene ligand, 2,7-di--butylpyrene-4,5,9,10-tetraone (pyrene), is now developed to synthesize a pair of dinuclear compounds {[CoL](pyrene)}[Co(CO)]·CHCl·2CHCH (, = 2, L = 1,10-phenanthroline, phen; , = 1.5, L = 2,2'-bipyridine, bpy). Variable-temperature magnetic susceptibilities and single-crystal X-ray diffraction measurements indicate a partial one-step valence tautomeric transition for and a rare two-step valence tautomeric transition for , respectively. DFT calculation results are consistent with the experimental data, revealing the correlation between thermodynamic parameters and the one-step/two-step valence tautomeric behaviors.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/acs.inorgchem.1c03944 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Pd(0)/Pd(II) Electromerism Triggered by Lewis Base Coordination to a Redox-Active Silicon Z-Type Ligand.
Angew Chem Int Ed Engl
December 2024
Anorganisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, 69120, Heidelberg, Germany.
Electromerism (aka. valence tautomerism) corresponds to the switching of electronic distributions between redox-active ligands and central elements. While this phenomenon is well established for several transition metals, the Pd(0)/Pd(II) couple could not yet be involved due to the high energy of the Pd(0) state.
View Article and Find Full Text PDFValence tautomerism, non-innocence, and emergent magnetic phenomena in lanthanide-organic tessellations.
Chem Commun (Camb)
January 2025
Department of Chemistry, Technical University of Denmark, DK-2800 Kgs. Lyngby, Denmark.
Coordination networks based on lanthanide ions entangle collective magnetic phenomena, otherwise only observed in inorganic 4f materials, and the tunable spatial and electronic structure engineering intrinsic to coordination chemistry. In this review, we discuss the use of 2D-structure-directing linear {LnI} nodes to direct the formation of polymeric coordination networks. The equatorial coordination plasticity of {LnI} results in broad structural diversity, including previously unobtainable tessellations containing motifs observed in quasicrystalline tilings.
View Article and Find Full Text PDFExpression of concern: Valence tautomeric interconversion of bis-dioxolene cobalt complex with imino-pyridine functionalized by TEMPO moiety in solid solutions with isostructural nickel analogue: phase transitions and monocrystal destruction.
Dalton Trans
November 2024
International Tomography Center of the SB of RAS, Institutskaya Str, 3a, Novosibirsk 630090, Russia.
Expression of concern for 'Valence tautomeric interconversion of bis-dioxolene cobalt complex with imino-pyridine functionalized by TEMPO moiety in solid solutions with isostructural nickel analogue: phase transitions and monocrystal destruction' by Michael P. Bubnov , , 2024, , 9151-9160, https://doi.org/10.
View Article and Find Full Text PDFOrigin of a Kinetically Selective Route for Thermoreversible Valence Tautomerism-Based Photoswitching in -Heterocycles Containing Conjugated Dienes.
J Org Chem
November 2024
Laboratory of Advanced Computation and Theory for Materials and Chemistry, Department of Chemistry, National Institute of Technology Warangal (NITW), Warangal, Telangana 506004, India.
The thermal electrocyclic ring opening of fused -cyclobutene to ,-diene is prohibited according to the Woodward-Hoffmann (WH) rules; nonetheless, experiments provide firm evidence for their formation. However, the mechanism, electronic structure, and behavior during the reaction are ambiguous. Herein, we attempt to gain insights into the mechanism of thermal ring opening in four -heterocycles containing a conjugated diene as the core skeleton.
View Article and Find Full Text PDFPutting the squeeze on valence tautomerism in cobalt-dioxolene complexes.
Nat Commun
October 2024
School of Molecular Sciences, University of Western Australia, Crowley, Western Australia, Australia.
Molecules that can reversibly switch between electronic states under an external stimulus are of interest to numerous applications. Complexes of open shell metal ions with redox active ligands undergo valence tautomerism, resulting in magnetic, colour and structural switching, relevant to data storage and actuators. However, the precise structural changes occurring during valence tautomerism in the solid state are unclear due to the lack of atomic-resolution characterization.
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!