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1,1'-Biolympicenyl: A Stable Non-Kekulé Diradical with a Small Singlet and Triplet Energy Gap.
J Am Chem Soc
September 2024
Institute of Molecular Plus, Department of Chemistry, Tianjin University and Haihe Laboratory of Sustainable Chemical Transformations, 92 Weijin Road, Tianjin 300072, China.
Dimerization of delocalized polycyclic hydrocarbon radicals is a simple and versatile method to create diradicals with tailored electronic structures and accessible high-spin states. However, the synthesis is challenging, and the stability issue of the diradicals remains a concern. In this study, we present the synthesis of a stable non-Kekulé 1,1'-biolympicenyl diradical using a protection-oxidation-protection strategy.
View Article and Find Full Text PDFDevelopment of (NO)Fe(NS) as a Metallodithiolate Spin Probe Ligand: A Case Study Approach.
Acc Chem Res
March 2024
Department of Chemistry, Texas A & M University, College Station, Texas 77843, United States.
ConspectusThe ubiquity of sulfur-metal connections in nature inspires the design of bi- and multimetallic systems in synthetic inorganic chemistry. Common motifs for biocatalysts developed in evolutionary biology include the placement of metals in close proximity with flexible sulfur bridges as well as the presence of π-acidic/delocalizing ligands. This Account will delve into the development of a (NO)Fe(NS) metallodithiolate ligand that harnesses these principles.
View Article and Find Full Text PDFA theory of the spin-crossover phenomena in the rare earth perovskite LaCoOinduced by temperature or a magnetic field.
J Phys Condens Matter
December 2023
ISIS Facility, STFC, Didcot, Oxfordshire OX11 0QX, United Kingdom.
Published magnetic data for LaCoOare successfully analyzed with coexistingand low-spin (LS) cobalt states. Energy levels of the two states are derived in analytic forms. To this end, fictitious orbital angular momentumof magnitude one defines the Γ() state.
View Article and Find Full Text PDFAttaining Exceptional Stable Copper(I) Metallacyclopentadiene Diradicaloids through Ligand Engineering.
Inorg Chem
November 2023
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350100, China.
Diradicaloids are generally high-energy molecules with open-shell configuration and are quite reactive. In this work, we report a feasible synthetic approach to attaining exceptionally stable copper(I) metallacyclopentadiene diradicaloids through ligand engineering. Copper(I)-hybrid cyclopentadiene diradicaloids - that absorb intensely in visible regions were successfully prepared in stoichiometrical yields under UV light irradiation.
View Article and Find Full Text PDFParamagnetic {[Fe(CO)]-μ-η:η-η:η-(C)} Dimer Bridged by Iron Atoms and C-C Bonds: Effect of Starting Iron Carbonyls on Structures and Properties of Negatively Charged Iron-Bridged Fullerene Dimers.
Inorg Chem
October 2023
Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry RAS, Chernogolovka, Moscow Region 142432, Russia.
The reaction between an excess of Fe(CO) with {Cryptand(K)}(C) produced the salt {Cryptand(K)}{[Fe(CO)]-μ-η:η-η:η-(C)}·4CHCl () containing negatively charged iron-bridged fullerene dimers. In these dimers, the C cages are linked via two Fe(CO) fragments, forming short Fe-C(C) bonds with a length of 2.070(3) Å and via two intercage C-C bonds with a length of 1.
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