The triplet benzene dianion is predicted to be aromatic based on Baird's rule. However, it has remained elusive due to the Jahn-Teller distortion. Herein, we report isolation of a benzene dianion with a triplet ground state in an inverse-sandwich europium benzene complex. Combined experimental and theoretical studies unveil that the strong antiferromagnetic coupling between the benzene dianion and 4f Eu ions is pivotal to the stabilization of the triplet state of the benzene dianion with Baird aromaticity. In addition, a comparison with analogous ytterbium benzene and europium -xylene complexes further reveals that the spin state of the benzene dianion depends on the spin-spin interaction and local symmetry. These results accomplish the isolation of the long-sought triplet benzene dianion and illustrate the effectiveness of spin modulation using lanthanide ions.
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http://dx.doi.org/10.1021/jacs.4c17459 | DOI Listing |
J Am Chem Soc
March 2025
Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. China.
The triplet benzene dianion is predicted to be aromatic based on Baird's rule. However, it has remained elusive due to the Jahn-Teller distortion. Herein, we report isolation of a benzene dianion with a triplet ground state in an inverse-sandwich europium benzene complex.
View Article and Find Full Text PDFSmall
January 2025
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore, 117543, Singapore.
Atomically precise open-shell graphene fragments, such as extended peri-acenes, hold significant interest for electronics and spintronics. However, their inherent high reactivity poses challenges for synthesis and application. In this study, a novel approach is introduced: the fusion of a zigzag-edged peri-tetracene with an all-armchair-edged hexa-peri-hexabenzocoronene (HBC) via two shared benzene rings to produce a stable open-shell hydrocarbon, named dibenzo-peri-heptacene (DBPH).
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Department of Chemistry, Michigan State University, 578 South Shaw Lane, East Lansing, Michigan, 48824, USA.
For the first time, the capture of the planar antiaromatic parent benzene dianion in between two trivalent rare earth (RE) metal cations (RE), each stabilized by two guanidinate ligands, is reported. The synthesized inverse-sandwich complexes [{(MeSi)NC(NPr)}RE](μ-η : η-CH), (RE=Y (1), Dy (2), and Er (3)) were crystallized from aprotic solvents and feature a remarkably planar parent benzene dianion, previously not encountered for any metal ion prone to low or absent covalency. The -2 charge localization at the benzene ligand was deduced from the results obtained by single-crystal X-ray diffraction analyses, spectroscopy, magnetometry, and Density Functional Theory (DFT) calculations.
View Article and Find Full Text PDFChem Commun (Camb)
July 2024
Research School of Chemistry, Australian National University, Canberra, ACT, Australia.
A porous three-component hydrogen bonded framework, 1⋅biphen⋅TP, was prepared from a tetra-amidinium component (1) and two different dianions, benzene-1,4-dicarboxylate (terephthalate, TP) and biphenyl-4,4'-dicarboxylate (biphen). Interestingly, when the framework was prepared in ethanol/water, 1⋅biphen⋅TP forms even when an excess of either dicarboxylate is present. However, when only water is used as solvent, only two-component frameworks are formed.
View Article and Find Full Text PDFChemistry
June 2024
School of Chemistry, Monash University, PO Box 23, 3800, Melbourne, Victoria, Australia.
In this contribution, we present "Birch-type", and other reductions of simple arenes by the potassium salt of an anionic magnesium dinitrogen complex, [{K(NON)Mg}(μ-N)] (NON=4,5-bis(2,4,6-tricyclohexylanilido)-2,7-diethyl-9,9-dimethyl-xanthene), which acts as a masked dimagnesium(I) diradical in these reactions. This reagent is non-hazardous, easy-to-handle, and in some cases provides access to 1,4-cyclohexadiene reduction products under relatively mild reaction conditions. This system works effectively to reduce benzene, naphthalene and anthracene through magnesium-bound "Birch-type" reduction intermediates.
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