Isolation of the elusive bisbenzimidazole Bbim3−˙ radical anion and its employment in a metal complex

The discovery of singular organic radical ligands is a formidable challenge due to high reactivity arising from the unpaired electron. Matching radical ligands with metal ions to engender magnetic coupling is crucial for eliciting preeminent physical properties such as conductivity and magnetism that are crucial for future technologies. The metal-radical approach is especially important for the lanthanide ions exhibiting deeply buried 4f-orbitals. The radicals must possess a high spin density on the donor atoms to promote strong coupling. Combining diamagnetic ⁸⁹Y (I = 1/2) with organic radicals allows for invaluable insight into the electronic structure and spin-density distribution. This approach is hitherto underutilized, possibly owing to the challenging synthesis and purification of such molecules. Herein, evidence of an unprecedented bisbenzimidazole radical anion (Bbim³⁻˙) along with its metalation in the form of an yttrium complex, [K(crypt-222)][(Cp*₂Y)₂(μ-Bbim˙)] is provided. Access of Bbim³⁻˙ was feasible through double-coordination to the Lewis acidic metal ion and subsequent one-electron reduction, which is remarkable as Bbim²⁻ was explicitly stated to be redox-inactive in closed-shell complexes. Two molecules containing Bbim²⁻ (1) and Bbim³⁻˙ (2), respectively, were thoroughly investigated by X-ray crystallography, NMR and UV/Vis spectroscopy. Electrochemical studies unfolded a quasi-reversible feature and emphasize the role of the metal centre for the Bbim redox-activity as neither the free ligand nor the Bbim²⁻ complex led to analogous CV results. Excitingly, a strong delocalization of the electron density through the Bbim³⁻˙ ligand was revealed via temperature-dependent EPR spectroscopy and confirmed through DFT calculations and magnetometry, rendering Bbim³⁻˙ an ideal candidate for single-molecule magnet design.

The long sought-after bisbenzimidazole radical was isolated through complexation to two rare earth metallocenes followed by reduction, and analysed through crystallography, VT EPR spectroscopy, electrochemistry, magnetometry, and DFT computations.     

Solvent-derived Fluorinated Secondary Interphase for Reversible Zn-graphite Dual-ion Batteries

The irreversibility of anion intercalation-deintercalation is a fundamental issue in determining the cycling stability of a dual-ion battery (DIB). In this work, we demonstrate that using a partially fluorinated carbonate solvent can drive a beneficial fluorinated secondary interphase layer formation. Such layer facilitates reversible anion (de−)intercalation processes by impeding solvent molecule co-intercalation and the associated graphite exfoliation. The enhanced reversibility of anion transport contributes to the overall cycling stability for a Zn-graphite DIB—a high Coulombic efficiency of 98.5 % after 800 cycles, with an attractive discharge capacity of 156 mAh g⁻¹ and a mid-point discharge voltage of ≈1.7 V (at 0.1 A g⁻¹). In addition, the formed fluorinated secondary interphase suppresses the self-discharge behavior, preserving 29 times of the capacity retention rate compared to the battery with a commonly used carbonate solvent, after standing for 24 hours. This work provides a simple and effective strategy for addressing the critical challenges in graphite-based DIBs and contributes to fundamental understanding to help accelerate their practical application.