We report that tetrathiatriarylmethyl (trityl) EPR probes are chiral molecules at room temperature, the two stereoisomers that differ in their helicity being configurationally stable enough to be separated and stored independently.
The organic metal-ion battery field
remains challenged by the lack
of high-voltage alkali-cation reservoir cathode materials. Whereas
a few recent breakthroughs provided valuable solutions for Li-ion
storage, Na-ion and K-ion organic reservoirs with high voltage and
ambient stability remain elusive. Herein, we show that the versatile
benzene-1,2,4,5-tetrayltetrakis methylsulfonyl-amide (PTtSA) tetra-anionic
framework displays universal performance for alkali cation storage.
The new synthesized Na4-PTtSA and K4-PTtSA phases
reversibly exchange two Na+ or K+ equivalents
per formula unit at redox potentials of 2.5 V vs Na+/Na
and 2.6 V vs K+/K, respectively. A singular comparative
analysis of Li-, Na-, and K-ion phases discloses the impact of the
alkali cation on the physicochemical properties, with direct impact
on the electrochemistry of the materials. This work not only offers
guidance and principles to tune the redox properties of organic redox
materials via spectator cations but also highlights
the versatility of organic materials for alkali cation storage.
The one-pot synthesis of useful [Pt 2 (0)(η 4 -1,6-diene) 3 ] complexes, directly from H 2 PtCl 6 ‚xH 2 O, has remained an unaddressed problem. We haVe found that the treatment of an i-PrOH solution of H 2 PtCl 6 ‚xH 2 O by (Me 3 SiO) 2 MeSi(CHdCH 2 ), in the presence of allyl ether (AE), followed by reaction of the in situ generated Pt(0) species with IPr carbene (IPr ) 1,3bis(2,6-diisopropylphenyl)imidazol-2-ylidene) enables the isolation of (IPr)Pt(AE) (1) in 50-70% yield. The scope of this method has been extended to other (L)Pt(1,6-diene) complexes (L ) 1,3-dicyclohexylimidazol-2-ylidene, triphenylphoshine; 1,6diene ) diethyl 2,2-diallylmalonate (DAM)), and the molecular structure of the (IPr)Pt(DAM) (4) complex has been unequiVocally determined by a single-crystal X-ray diffraction analysis. These results are significant for the formation of actiVe L-Pt-(0) fragments in catalysis.
In the rising advent of organic Li-ion positive electrode materials with increased energy content, chemistries with high redox potential and intrinsic oxidation stability remain a challenge. Here, we report the solid-phase reversible electrochemistry of the oximate organic redox functionality. The disclosed oximate chemistries, including cyclic, acyclic, aliphatic, and tetra-functional stereotypes, uncover the complex interplay between the molecular structure and the electroactivity. Among the exotic features, the most appealing one is the reversible electrochemical polymerization accompanying the charge storage process in solid phase, through intermolecular azodioxy bond coupling. The best-performing oximate delivers a high reversible capacity of 350 mAh g
−1
at an average potential of 3.0 versus Li
+
/Li
0
, attaining 1 kWh kg
−1
specific energy content at the material level metric. This work ascertains a strong link between electrochemistry, organic chemistry, and battery science by emphasizing on how different phases, mechanisms, and performances can be accessed using a single chemical functionality.
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