A series of heterobimetallic wire-like organometallic complexes [( tpy-CH-R)(PPh)Ru-C≡C-Fc] ( tpy-CH-R = 4'-(aryl)-2,2':6',2''-terpyridyl, Fc = [(η-Cp)Fe], R = -H, -Me, -F, -NMe in complexes 5-8, respectively) featuring ferrocenyl and 4'-(aryl)-2,2':6',2''-terpyridyl ruthenium(II) complexes as redox active metal termini, have been synthesized. Various spectroscopic tools, such as multinuclear NMR, IR spectra, HRMS, CHN analyses, and single crystal X-ray crystallography have been utilized to characterize the heterobimetallic complexes. The electrochemical and UV-vis-NIR spectroscopic studies have been investigated to evaluate the electronic delocalization across the molecular backbones of the Ru(II)-Fe(II) heterobinuclear organometallic dyads. Electrochemical studies reveal two well-separated reversible redox waves as a result of successive oxidation of the ferrocenyl and Ru(II) redox centers. The spin density distribution analyses reveal that the initial oxidation process is associated with the Fe(II)/Fe(III) couple followed by one electron oxidation of the ruthenium(II) center. The high K value (0.11-1.73 × 10) and intense NIR absorption, with molar absorption coefficient (in the order of 10 M cm) for the RuFe mixed-valence species, signify strong electronic communication between the two metal termini. The electronic coupling constant ( H) has been estimated to be 492 and 444 cm for the structurally characterized complexes 6 and 7, respectively. The redox and NIR absorption features indicate that the mixed-valence system of the heterobinuclear dyads belongs to a Robin and Day "class II" system.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/acs.inorgchem.8b02440 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Metal-Translocation-Coupled Ligand-Binding/Release by Dinuclear Rhodium Sandwich Complexes.
Chemistry
January 2025
Institute of Science Tokyo, Department of Chemical Science and Engineering, O-okayama, 152-8552, Meguro-ku, JAPAN.
Switching the location of metal atoms or ions in a molecule has been of great interest as a behavior of molecular machines. We describe herein that the reversible metal translocation can be coupled with the ligand-binding/release of organometallic complexes. The two rhodium moieties sandwiched between arylpolyene ligands exhibit metal-assembly and disassembly through reversible migration between the arene site and the olefin site, in response to the association and dissociation of additional ligands.
View Article and Find Full Text PDFSingle-molecule Magnet Properties of Silole- and Stannole-ligated Erbium Cyclo-octatetraenyl Sandwich Complexes.
Chemistry
January 2025
University of Sussex, Department of Chemistry, School of Life Sciences, BN1 9QJ, Brighton, UNITED KINGDOM OF GREAT BRITAIN AND NORTHERN IRELAND.
The synthesis, structures and magnetic properties of an η5-silole complex and an η5-stannole complex of erbium are reported. The sandwich complex anions [(η5-CpSi)Er(η8-COT)]- and [(η5-CpSn)Er(η8-COT)]-, where CpSi is [SiC4-2,5-(SiMe3)2-3,4-Ph2]2- (1Si), CpSn is [SnC4-2,5-(SiMe3)2-3,4-Me2]2- (1Sn) and COT = cyclo-octatetraenyl, were obtained as their [K(2.2.
View Article and Find Full Text PDFSynthesis and Evaluation of Cytotoxic Activity of RuCp(II) Complexes Bearing (Iso)nicotinic Acid Based Ligands.
Pharmaceuticals (Basel)
January 2025
Centro de Química Estrutural, Institute of Molecular Sciences, Faculdade de Ciências, Universidade de Lisboa, Campo Grande, 1749-016 Lisboa, Portugal.
Background/objectives: Cancer remains one of the major challenges of our century. Organometallic ruthenium complexes are gaining recognition as a highly promising group of compounds in the development of cancer treatments.
Methods: Building on the auspicious results obtained for [Ru(η-CH)(PPh)(bipy)][CFSO] (TM34), our focus has shifted to examining the effects of incorporating bioactive ligands into the TM34 framework, particularly within the cyclopentadienyl ring.
Advanced flame-retardant biocomposites: Polylactic acid reinforced with green gallic acid‑iron‑phosphorus coated flax fibers.
Int J Biol Macromol
January 2025
Department of Chemical Engineering Materials Environment, Sapienza University of Rome, Via Eudossiana 18, 00184 Rome, Italy.
This study introduces a sustainable approach for enhancing the fire retardancy and smoke suppression of poly(lactic acid) (PLA) composites, contributing to addressing one of the major challenges in biocomposites that limits their application in various engineering fields, as automotive and construction sectors. Flax fibers (FF) were surface functionalized with a novel organic-inorganic hybrid flame retardant (FR), offering a sustainable bioinspired approach that mitigates potential mechanical properties impairment and FR leaching, which can cause environmental concerns and reduced composite durability. The process involves a three-step coating procedure.
View Article and Find Full Text PDFPalladium-Catalyzed Oxidative Allene-Allene Cross-Coupling.
J Am Chem Soc
January 2025
Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, SE-10691 Stockholm, Sweden.
Direct cross-coupling reactions between two similar unactivated partners are challenging but constitute a powerful strategy for the creation of new carbon-carbon bonds in organic synthesis. [4]Dendralenes are a class of acyclic branched conjugated oligoenes with great synthetic potential for the rapid generation of structural complexity, yet the chemistry of [4]dendralenes remains an unexplored field due to their limited accessibility. Herein, we report a highly selective palladium-catalyzed oxidative cross-coupling of two allenes with the presence of a directing olefin in one of the allenes, enabling the facile synthesis of a broad range of functionalized [4]dendralenes in a convergent modular manner.
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!