The applicability of organic battery materials in conventional rocking-chair Li-ion cells remains deeply challenged by the lack of lithium-containing and air stable organic positive electrode chemistries. Decades-long experimental and theoretical research in the field resulted in only few recent examples of Li-reservoir materials, all relying on the archetypal carbonyl redox chemistry. Here, we extend the chemical space of organic Li-ion positive electrode materials with a new class of conjugated sulfonamides (CSA) and show that the electron delocalization on the sulfonyl groups endows the resulting CSAs with intrinsic oxidation and hydrolysis resistance while handled in ambient air, yet displaying reversible electrochemistry for charge storage. The formal redox potential of the uncovered CSAs chemistries spans a wide range between 2.85 -3.45 V (vs. Li + /Li 0 ), finely tuneable through electrostatic or inductive molecular design. This class of organic Li-ion positive electrode materials is the first one to consequentially challenge the inorganic battery cathodes realm, as this first generation of CSA chemistries already displays gravimetric energy storage metrics comparable to those of stereotypical LiFePO4.

Raising the operating potential of the organic positive electrode materials is a crucial challenge if they are to compare with lithium-ion inorganic counterparts. Although many efforts have been directed on tuning through substituent electronic effect, the chemistries than can operate above 3 V vs Li + /Li 0 , and thus be air stable in the Li-reservoir form (alike the conventional inorganic Liion positive electrode materials) remain finger-counted. Herein, we report on a new n-type organic Li-ion positive electrode materialthe tetralithium 2,5dihydroxy-1,4-benzenediacetatewith a remarkably high redox potential of 3.35 V vs Li + /Li attained notably in the solid phase. The origin of the high-energy content in this quinone derivative is found in a stereoelectronic chameleonic effect with an intramolecular conformation change and charge modulation leading to a redox potential increase of 650 mV in the solid state as compared to the same chemistry tested in solution (2.70 V vs Li + /Li). The conformational dependent electroactivity rationale is supported by electrochemical and crystallography analysis, comparative infrared spectroscopy, and DFT calculation. We identify and make a linear correlation between the enolate vibrational modes and the redox potential, with general applicability for possibly other phenolate redox chemistries. Owing to these effects, this lithiated quinone is stable in ambient air and can be processed and handled alike the conventional inorganic Li-ion positive electrode materials. Whereas intrinsic to high voltage operation stability issues remain to be solved for practical implementation, our fundamental in nature and proof-of-concept study highlights the strong amplitude of through-space charge modulation effects in designing new organic Li-ion positive electrode chemistries with practical operating potential. 46For all these reasons, the organic battery field has 47

Coordination polymers (CPs) made of redox-active organic moieties and metal ions emerge as an important class of electroactive materials for battery applications.

The geometrical properties and electronic structure of single DNA nucleosides (deoxyadenosine, deoxythymidine, deoxyguanosine, deoxycytidine) adsorbed on a metallic surface of Au(100) are determined using density functional theory computations. We investigate multiple adsorption geometries and the resulting molecule−surface interaction mechanisms. For adenosine, we found negligible differences between the binding energy in the two configurations investigated by us, while for guanosine this difference reaches the maximum value among the four nucleosides (i.e., 0.38 eV). The projected density of states indicates that the physisorption is the main cause of the binding energy. Nevertheless, for the adsorbed deoxycytosine (dC), we point out the presence of the chemical interaction too. While the absolute values of the molecule−surface charge transfer are small, they are qualitatively dependent on the orientation of the nucleosides to the surface. If the DNA bases are oriented perpendicular to the surface, the electronic population of molecules decreases, while the parallel orientation of the DNA bases with respect to metal surface leads to an increase of electronic population on the molecules.

We compare the density functional theory (DFT) results on the adsorption of small aromatic molecules (benzene, pyridine and thiophene) on gold surfaces obtained by using three types of van der Waals exchange-correlation functionals and localized basis set calculations. We show that the value of the molecule-surface binding energy depends on the interplay between the BSSE effect and the tendency of the exchange-correlation functionals to overestimate both the molecule-surface as well as the gold-gold distances within the relaxed systems. Consequently, we find that by using different types of LCAO basis sets or geometric models for the adsorption of the molecules on the surface, the binding energy can vary up to 100 %. A critical analysis of the physical parameters resulting from the calculations is presented for each exchange-correlation functional.