Polyanionic Chains Research Articles

Oppositely charged polymer-surfactant nanoparticles stabilized by triblock copolymers for enhanced oil loading

When oppositely charged polymers and surfactants combine, they can form a concentrated phase rich in micelles interconnected by polymer chains. Dispersing this concentrated phase as nanoparticles in an aqueous media can be a way to load and deliver hydrophobic ingredients. This study employed triblock copolymers of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide), EOxPOyEOx, also known as poloxamers or pluronics, to disperse the concentrated phase, forming nanoparticles of aggregated micelles connected by the polyion chains. We showed that nanoparticles formed by hexadecyltrimethylammonium bromide (CTAB), poly(acrylic acid) (PAA), and different EOxPOyEOx copolymers can enhance the loading of oily ingredients compared to pure surfactant micelles. Dispersions with 1.6 wt% of nanoparticles exhibited water-like viscosity and loaded up to 0.48 wt% of oil. Characterization techniques, including dynamic light scattering (DLS), electrophoretic mobility, small-angle X-ray scattering (SAXS), and cryogenic transmission electronic microscopy (cryo-TEM), revealed positively charged spherical 50–180 nm nanoparticles with a core formed by concentrated micelles, that were stable for at least 4 months. Variations in the EO and PO block lengths did not impact morphology, showing that different EOxPOyEOx copolymers were suitable for dispersing the nanoparticles. Increasing EO block length size decreased the diameter of nanoparticles and enhanced stability, providing a means to control their properties. In conclusion, nanoparticles formed by oppositely charged polymer-surfactant mixtures and stabilized by triblock copolymers showed potential for applications, such as sprays, due to their effective oil loading, high stability, and facile preparation.

Dendrite-free, long cycle life Zn–MnO2 battery based on a polyanionic hydrogel electrolyte by constructing transfer channels and regulating solvation structure

Aqueous zinc ion batteries (AZIBs) are highly regarded as new generation of energy storage devices because of low cost and environmental friendliness. Particularly, flexible AZIBs with hydrogel electrolytes are suitable candidates for wearable electronics. However, continuous water-induced side reactions, uncontrolled dendrites and trade-off of electrochemical performances with mechanical strength are still obstacles for high-performance AZIBs. To address these issues, we designed a polyanionic hydrogel electrolyte (PAPHE) with sulfonate monomers and polyethylene glycol diacrylate (PEGDA) as crosslinker. Due to the electrostatic interactions between Zn2+ and sulfonate ions, Zn2+ can migrate along polyanionic chains. Meanwhile, electronegative oxygen atoms in PEGDA also interact with Zn2+ and weaken electrostatic interactions. The transfer channels are formed with “wall” of polyanion chains and PEGDA. Moreover, both sulfonate ions and ether bonds on the “wall” can regulate the solvation structure to reduce the activity of water, inhibiting side reactions, corrosion or by-products. Therefore, the PAPHE shows satisfying conductivity of 16.38 mS cm−1, stable Zn plating/stripping over 1600 h, flexibility and high compressive resistance (0.501 MPa at strain of 50 %). The Zn||PAPHE||MnO2 cells deliver good specific capacity of 274.5 mAh g−1 and can cycle over 1800 times. The pouch-cell can also work stably under various deformations.

A Robust Hydrogel Electrolyte with Ultrahigh Ion Transference Number Derived from Zincophilic “Chain‐Gear” Network Structure for Dendrite‐Free Aqueous Zinc Ion Battery

AbstractAs a promising energy storage device, an aqueous zinc ion battery (AZIB) still suffers dendrite growth, hydrogen evolution, and corrosion. Hydrogel electrolyte solves the above issues to some extent. Nevertheless, the mechanical properties of most hydrogel electrolytes are not competitive enough to meet booming demand for flexible electronics. In this work, a robust “chain‐gear” hydrogel electrolyte (PM‐HE) crosslinked by polymeric micelles (PMs) is constructed, in which PMs serve as “gears” and form “chain‐gear” structure with polyanion chains. Specifically, “gears” support molecular chains, constructing hierarchically porous structures and opening up paths for Zn2+. Apart from as crosslinkers, PMs exist competitive mechanism with polyanion chains to promote ion decoupling. Such a “chain‐gear” structure can realize desolvation and accelerate ion transport. Thereby, PM‐HE possesses excellent ionic conductivity (60.6 mS cm−1) and ultrahigh transference number (0.88). Symmetrical cells can realize stable cycling over 1500 h with Zn uniform deposition. Remarkably, PM‐HE has excellent tensile (0.23 MPa) and compressive (11.3 MPa) properties profited from strengthening and toughening effect of PMs. The flexible battery can supply power stably under harsh conditions. This work proposes the strategy of constructing an all‐around hydrogel electrolyte based on reasonable design in network structure, providing more possibilities for the practical application of flexible AZIB.

Improving Photoelectron Localization to Significantly Enhanced Broadband Orange‐Light Emission in Hybrid Antimony Halides with Sb─Cl Secondary Bonding

AbstractHybrid ns2 metal halides have attracted extensive attention due to the unique photophysical behavior. However, the reasonable improvement of photoluminescence efficiency by accurate structural modulation remains a great challenge. Herein, two kind of antimony halides with formulae as (S)/(R)‐[C6H16N2]3[SbCl5]2·2Cl ((S)/(R)‐1·2Cl) and (S)/(R)‐[C6H16N2]2[SbCl5]2 ((S)/(R)‐2) ([C6H16N2]2+ = 1,2‐Diaminocyclohexane) are developed, in which 0D [Sb4Cl20]8− clusters and 1D infinite [SbCl5]n2n− polyanion chains are adopted, respectively. The stoichiometric tunability enables metastable (S)/(R)‐1·2Cl being transformed to dynamic stable (S)/(R)‐2. All compounds contain a large number of Sb─Cl secondary bonds because of the strong chemical activity of 5s2 electrons. The obtained compounds exhibit broadband orange‐light emission, while photoluminescence quantum yield of (S)/(R)‐2 is significantly enhanced to ≈76% due mainly to the generation of more localized electrons onto 1D chains. Experimental and computational results reveal that efficient broadband emission derives from the synergistic emission of singlet and triplet states, where the presence of shallow trap energy levels leads to anti‐thermal quenching behavior. Furthermore, the highly efficient photoluminescence property allows (S)‐2 to become excellent down‐conversion phosphor for white‐light emitting diode. This work proves that exploring structure‐property relationship in hybrid systems is helpful in promoting the rapid development of high‐performance broadband emission metal halides.

Dimension and Flexibility of Polystyrenesulfonate Chains in Methanol-Water.

The influence of the relative permittivity of the solvent medium on the single-chain dimension and flexibility of sodium polystyrenesulfonate chains has been investigated in mixed solvent media of methanol and water using viscosity experiments. Particular attention has been paid to explore the effect of the added low-molar-mass electrolyte. The root-mean-square (rms) radii of gyration of the chains in the unperturbed state have been calculated by applying the Flory model, while the intrinsic persistence lengths by the Benoit-Doty equation on the basis of the Kratky-Porod worm-like chain model. Estimation of the expansion factors for the rms radius of gyration, and the electrostatic persistence length helps evaluate the rms radii of gyration and the total persistence length of polystyrenesulfonate chains in the presence of varying amount of the supporting electrolyte. The polyion chains are highly extended at low ionic strengths but exhibit coil-like behavior with small persistence lengths when an excess of the supporting electrolyte is added in all the methanol-water mixtures investigated. Specifically, in the investigated solvent media, the polystyrenesulfonate chains have been found to shrink by ∼63-65% in the θ-state from their expanded conformation in the presence of 0.0001 mol L-1 NaCl. The chain dimensions pass through a maximum as the medium becomes richer in methanol, which could be explained by the formation and breakup of internal rings involving the polyion chain and water and/or methanol molecules. The intrinsic persistence length of sodium polystyrenesulfonate in a methanol-water mixture containing 0.1 mole fraction of methanol is ca. 1.3 times that in a medium with 0.3 mole fraction of methanol, indicating that flexibility of the polyion depends appreciably on the relative permittivity of the medium.

Electron Localization Induced by Disordered Anions in an Organic Conductor.

We report on a new organic conductor κ″-(ET)2Cu[N(CN)2]Br (κ″-Br), which is the first polymorph of an organic superconductor κ-(ET)2Cu[N(CN)2]Br (κ-Br), where ET denotes bis(ethylenedithio)tetrathiafulvalene. κ″-Br has a similar κ-type arrangement of ET molecules to κ-Br, but, in contrast to the orthorhombic κ-Br, which has ordered polyanion chains, presents a monoclinic crystal structure with disordered polymeric anion chains. To elucidate the electronic state of κ″-Br, we performed band calculations as well as transport, magnetic, and optical measurements. The calculated band dispersion, magnitude of electron correlation, and room-temperature optical conductivity spectra of κ″-Br were comparable to those of κ-Br. Despite these similarities, the κ″-Br salt exhibited a semiconducting behavior. The electron spin resonance and Raman spectroscopies indicated that there is neither magnetic nor charge order in κ″-Br, suggesting the occurrence of Anderson localization due to disordered anion layers.

Polysaccharide/Carbon Quantum Dots Composite Film on Model Colloidal Particles-An Electro-Optical Study.

Negatively charged carbon dots (Cdots) were successfully impregnated into chitosan/alginate film formed on model colloidal particles as a result of the attractive interactions with the chitosan molecules. The electrical properties of the produced films were studied by electrokinetic spectroscopy. In this study, the electric light scattering method was applied for first the time for the investigation of suspensions of carbon-based structures. The electro-optical behavior for the suspension of polymer-coated particles showed that the electric polarizability of the particle-covered layer from alginate was significantly higher compared to that of the layer from chitosan due to the higher charge density of alginate. The presence of a low concentration of Cdots in the film results in partial charge screening. It was confirmed that the polarizability of counterions with lower mobility along the adsorbed polyion chains was responsible for the registered electro-optical effect from the suspension of polymer-coated particles and that the participation of diffuse H+ counterions of Cdots in the creation of the electro-optical effect was negligible. The observed oscillation behavior in the evolution of the film thickness was interpreted through the participation of compensatory effects due to the additional adsorption/desorption of polyelectrolyte complexes from the film surface. The concentration of Cdots in the film was determined, and the loaded amount was ca. 6.6 µg/mL per layer.

Highly Ordered Thermoplastic Polyurethane/Aramid Nanofiber Conductive Foams Modulated by Kevlar Polyanion for Piezoresistive Sensing and Electromagnetic Interference Shielding

HighlightsKevlar polyanionic chains induced the formation of highly ordered porous thermoplastic polyurethane foams with adjustable pore sizes.A tiny amount of Ti3C2Tx MXene was performed as reducing agent for the electroless deposition of copper nanoparticles.The conductive foam reinforced by aramid nanofibers exhibited excellent piezoresistive sensing and electromagnetic interference shielding performance.

Encapsulating melittin from animal venom by finely tuned charge compensation with polymer carriers

Due to their wide availability, polypeptide/protein venoms produced by certain insects are of high interest as potential active pharmacological ingredients; however, the number of clinical studies on these venoms remains poor. In this paper, we describe an extremely efficient platform to form polyplexes from cationic amphiphilic animal venoms, such as the hemolytic poison melittin. The idea is based on supramolecular melittin cationic charge compensation with nanoparticles (micelles composed of hydrophobic glassy polystyrene core and hydrophilic poly(meth)acrylic acid corona, PMA and PAA acid homopolymers) with high anion charge density at physiological pH. An instant “mix and go” process and efficient melittin complexation with nanoparticles at concentrations down to micrograms per milliliter of PBS solution was achieved and proven by inhibition of melittin-induced hemolysis. We studied in detail how the structural features of the nanoparticles influence their potency; we found that the most important parameter is the number of carboxylates in the polyanion chain (proportional to the molecular weight and length of the anionic poly(meth)acrylic acid block). The poly(meth)acrylic acid-based polymer nanoparticles may be useful as melittin (and possibly other cationic amphiphilic animal venoms) antidotes but also as models for constructing future delivery systems to apply the venoms therapeutically.

Concentrated Nonaqueous Polyelectrolyte Solutions: High Na-Ion Transference Number and Surface-Tethered Polyanion Layer for Sodium-Metal Batteries.

Na metal is a promising anode material for the preparation of next-generation high-energy-density sodium-ion batteries; however, the high reactivity of Na metal severely limits the choice of electrolyte. In addition, rapid charge-discharge battery systems require electrolytes with high Na-ion transport properties. Herein, we demonstrate a stable and high-rate sodium-metal battery enabled by a nonaqueous polyelectrolyte solution composed of a weakly coordinating polyanion-type Na salt, poly[(4-styrenesulfonyl)-(trifluoromethanesulfonyl)imide] (poly(NaSTFSI)) copolymerized with butyl acrylate, in a propylene carbonate solution. It was found that this concentrated polyelectrolyte solution exhibited a remarkably high Na-ion transference number (tNaPP = 0.9) and a high ionic conductivity (σ = 1.1 mS cm-1) at 60 °C. Furthermore, the surface of the Na electrode was modified with polyanion chains anchored via the partial decomposition of the electrolyte. The surface-tethered polyanion layer effectively suppressed the subsequent decomposition of the electrolyte, thereby enabling stable Na deposition/dissolution cycling. Finally, an assembled sodium-metal battery with a Na0.44MnO2 cathode demonstrated an outstanding charge/discharge reversibility (Coulombic efficiency >99.8%) over 200 cycles while also exhibiting a high discharge rate (i.e., 45% capacity retention at 10 mA cm-2).

Syndecan-4 Mediates the Cellular Entry of Adeno-Associated Virus 9

Due to their low pathogenicity, immunogenicity, and long-term gene expression, adeno-associated virus (AAV) vectors emerged as safe and efficient gene delivery tools, over-coming setbacks experienced with other viral gene delivery systems in early gene therapy trials. Among AAVs, AAV9 can translocate through the blood-brain barrier (BBB), making it a promising gene delivery tool for transducing the central nervous system (CNS) via systemic administration. Recent reports on the shortcomings of AAV9-mediated gene delivery into the CNS require reviewing the molecular base of AAV9 cellular biology. A more detailed understanding of AAV9's cellular entry would eradicate current hurdles and enable more efficient AAV9-based gene therapy approaches. Syndecans, the transmembrane family of heparan-sulfate proteoglycans, facilitate the cellular uptake of various viruses and drug delivery systems. Utilizing human cell lines and syndecan-specific cellular assays, we assessed the involvement of syndecans in AAV9's cellular entry. The ubiquitously expressed isoform, syndecan-4 proved its superiority in facilitating AAV9 internalization among syndecans. Introducing syndecan-4 into poorly transducible cell lines enabled robust AAV9-dependent gene transduction, while its knockdown reduced AAV9's cellular entry. Attachment of AAV9 to syndecan-4 is mediated not just by the polyanionic heparan-sulfate chains but also by the cell-binding domain of the extracellular syndecan-4 core protein. Co-immunoprecipitation assays and affinity proteomics also confirmed the role of syndecan-4 in the cellular entry of AAV9. Overall, our findings highlight the universally expressed syndecan-4 as a significant contributor to the cellular internalization of AAV9 and provide a molecular-based, rational explanation for the low gene delivery potential of AAV9 into the CNS.

Synthesis of methacrylate polyanion chains via RAFT polymerization, kinetic study. Thermal properties of its copolymers with MMA and monomers’ reactivity ratios

Polyanionic chains, in which multiple monomeric units bear anion groups as counter ions to Li+, are excellent candidates for the preparation of polymer-based electrolytes, where anion movement is restricted, while lithium ions are free to move in the polymer matrix The aforementioned, are characterized as single Li-ion polymer electrolytes, and a great research effort is currently focused on the controlled synthesis and molecular characterization of such materials. Herein, we report the synthesis of Potassium 3-sulfonyl (trifluoromethane sulfonyl) imide propyl methacrylate (MASTFSIK) ionic monomer and its controlled polymerization kinetics, using RAFT techniques, while the progression of polymer tacticity is also noted in relation to the molecular weight of the growing polyanionic chains. The ion – exchange reaction with LiClO4 can be used to obtain the lithiated analog (PMASTFSILi). A series of linear copolymers (PMMA-co-PMASTFSILi) was synthesized with comparable degree of polymerization and varying compositions, considering the different monomeric units, for their thermal properties to be evaluated. The data suggest the presence of strong ionic interactions within the polymer matrix, resulting in a significant increase of the glass transition temperature for the polyanionic samples. The reactivity ratios of the MMA, MASTFSIK monomers were studied with various methods (FR, inv FR, KT, COPOINT), showing a preferential propagation of the MASTFIK monomer at low monomer consumption.

Shaping polyelectrolyte composites for heavy metals adsorption from wastewater: Experimental assessment and equilibrium studies

Design of core/shell composite microparticles for loading/release of organic/inorganic pollutants is of great interest in wastewater treatment. As compared to the classic layer-by-layer strategy, the new approach presented in this study introduced higher organic shell amounts in one-pot deposition step, with less material and energy consumption and lack of toxic by-products formation. Herein, one weak polycation (polyethyleneimine) and two weak polyanions were directly deposited onto silica surface through precipitation of an in-situ formed interpolyelectrolyte coacervate, followed by selective crosslinking with glutaraldehyde and extraction of polyanion chains, confirmed by electrokinetic measurements and FTIR spectra of composites. Twelve composite sorbents were synthesized and tested for adsorption of cadmium, as model heavy metal ion. It was demonstrated that the high sorption occurred onto four newly synthesized composites which is correlated to the deposited shell amount, dependent on the deposition method, polyanion nature and crosslinking ratio. The Cd2+ sorbed amount increased with the polyelectrolyte deposited amount and with the accessibility toward active sorption site, less cross-linked composite shells sorbing higher amounts as compared to strong cross-linked shells, the molar ratio [active site]:[Cd2+] ranging from 16:1 to 26:1. The best fitting of four isotherm (Langmuir, Freundlich, Sips and Toth) and four kinetics (pseudo-first order, pseudo-second order, modified Freundlich and Elovich) models was assessed by the sum of normalized errors, based on different nonlinear regression error functions, and by the Hannah-Quinn information criterion. In general, the best agreement with the experimental data was found for Toth isotherm and the pseudo-second order kinetic model. Efficient regeneration of the sorbents was possible at least three times. The competitive effect of Pb2+ and Ni2+ ions was also studied in simulated and real systems. Silica composite sorbents with polyethyleneimine chains as major component of the shell could be very promising in wastewater treatment processes.

Rheological behavior of multi-sized SiC inks containing polyelectrolyte complexes specifically for direct ink writing

In order to simultaneously improve both the solid loading and rheological behavior of ceramic ink during direct ink writing (DIW) process, the polyelectrolyte complexes have been used as rheological modifiers. Based on the Funk-Dinger function, the maximum solid loading of multi-sized SiC ink reached 63 vol%. The viscoelasticity of SiC inks with different [COOH]:[NHx] molar ratios was investigated and the mechanism of polyionic chains on rheology was analyzed. When the [COOH]:[NHx] molar ratio was 1:0.1, the SiC ink exhibited excellent thixotropic behavior and formability. The effect of particle size on rheological behavior of SiC ink was investigated to clarify the correlation between polyelectrolyte complexes and multi-sized SiC.

Li-Ion Transport and Solvation of a Li Salt of Weakly Coordinating Polyanions in Ethylene Carbonate/Dimethyl Carbonate Mixtures.

Electrolytes with a high Li-ion transference number (tLi) have attracted significant attention for the improvement of the rapid charge-discharge performance of Li-ion batteries (LIBs). Nonaqueous polyelectrolyte solutions exhibit high tLi upon immobilization of the anion on a polymer backbone. However, the transport properties and Li-ion solvation in these media are not fully understood. Here, we investigated the Li salt of a weakly coordinating polyanion, poly[(4-styrenesulfonyl)(trifluoromethanesulfonyl)amide] (poly(LiSTFSA)), in various ethylene carbonate and dimethyl carbonate mixtures. The highest ionic conductivity was unexpectedly observed for the lowest polar mixture at the highest salt concentration despite the low dissociation degree of poly(LiSTFSA). This was attributed to a unique conduction phenomenon resulting from the faster diffusion of transiently solvated Li ions along the interconnected aggregates of polyanion chains. A Li/LiFePO4 cell using such an electrolyte demonstrated improved rate capability. These results provide insights into a design strategy of nonaqueous liquid electrolytes for LIBs.

Syndecan-4 Is a Key Facilitator of the SARS-CoV-2 Delta Variant's Superior Transmission.

Emerging SARS-CoV-2 variants pose threats to vaccination campaigns against COVID-19. Being more transmissible than the original virus, the SARS-CoV-2 B.1.617 lineage, named the Delta variant, swept through the world in 2021. The mutations in the Delta’s spike protein shift the protein towards a net positive electrostatic potential. To understand the key molecular drivers of the Delta infection, we investigate the cellular uptake of the Delta spike protein and Delta spike-bearing SARS-CoV-2 pseudoviruses. Specific in vitro modification of ACE2 and syndecan expression enabled us to demonstrate that syndecan-4, the syndecan isoform abundant in the lung, enhances the transmission of the Delta variant by attaching its mutated spike glycoprotein and facilitating its cellular entry. Compared to the wild-type spike, the Delta one shows a higher affinity towards heparan sulfate proteoglycans than towards ACE2. In addition to attachment to the polyanionic heparan sulfate chains, the Delta spike’s molecular interactions with syndecan-4 also involve syndecan-4’s cell-binding domain that mediates cell-to-cell adhesion. Regardless of the complexity of these interactions, exogenously added heparin blocks Delta’s cellular entry as efficiently as syndecan-4 knockdown. Therefore, a profound understanding of the molecular mechanisms underlying Delta infections enables the development of molecularly targeted yet simple strategies to reduce the Delta variant’s spread.

Quasi-1D electronic transport and isotropic phonon transport in the Zintl Ca5In2Sb6

Crystals with anisotropic thermoelectric transport coefficients can yield a high figure-of-merit along the direction with the highest electronic mobility, provided the Seebeck coefficient and thermal conductivity are relatively isotropic. In this study, we combine experiment and theory to investigate the anisotropic properties of the quasi-1D Zintl phase Ca5In2Sb6. Ca5In2Sb6 is predicted by ab initio calculations to have extremely anisotropic p-type electrical conductivity and power factor, arising from light effective mass parallel to its ladder-like polyanionic chains. In contrast, the Seebeck coefficient and lattice thermal conductivity are predicted to be relatively isotropic. The latter is evidenced by the nearly isotropic computed speed of sound tensor and experimentally obtained thermal expansion coefficients. In order to characterize the anisotropic electrical conductivity, Ca5In2Sb6 single crystals were grown from an In–Sb rich molten flux and measured both parallel and perpendicular to the polyanionic chains. Due to the small crystal cross-sections, measurements perpendicular to the growth direction demanded a novel photolithography methodology whereby micro-ribbons were extracted using focused ion beam milling, and processed using laser photolithography to deposit contacts for electrical resistivity and Hall coefficient measurements. The conductivity parallel to the growth direction was found to be nearly 20x higher than the perpendicular direction, in agreement with our theoretical predictions. This study represents one of the first experimental confirmations of highly anisotropic electrical conductivity in Zintl thermoelectrics.

KSb(BeF3)F3: a totally fluorine strategy for achieving wide bandgap and large birefringence

A novel fluoroberyllate KSb(BeF3)F3 featuring unique [BeF3]∞− polyanion chains was successfully developed via a totally fluorine strategy, which endows it with a wide bandgap (5.3 eV) and large birefringence (0.11@546 nm).

Influence of divalent ions on composition and viscoelasticity of polyelectrolyte complexes

AbstractThe addition of monovalent salts to polyelectrolyte complexes (PECs) comprising oppositely charged polyelectrolytes results in diminishing propensity for complexation, leading to complexes with higher water contents and lower moduli. However, the corresponding influence of multivalent ions on polyelectrolyte complexation has not yet been explored beyond enhanced screening effects. Here, we elucidate the significant impact of the valency of the salt cation on the composition, ion partitioning, and viscoelasticity of charge‐matched PECs comprising sodium salt of poly(acrylic acid) and poly(allylamine hydrochloride). Notably, preferential partitioning of divalent cations (Ca2+ and Sr2+) into the complexes is observed, in stark contrast to the depletion of monovalent ions (Na+) from the complexes. Concomitantly, electrostatic bridging of polyanion chains by divalent ions is found to hinder their relaxation, manifesting as a non‐monotonic evolution of the shear moduli of the complexes with increasing divalent salt concentrations. Relatedly, a failure of time‐salt and time‐ionic strength superposition approaches in presence of divalent ions is demonstrated, highlighting the nontrivial influence of these ions on chain relaxation behavior.

Anion⋅⋅⋅Anion Interactions Involving σ-Holes of Perrhenate, Pertechnetate and Permanganate Anions.

In this communication experimental and theoretical results are reported affording strong evidence that interactions between electron rich atoms and the metal of tetroxide anions of group 7 elements are a new case of attractive and σ‐hole interactions. Single crystal X‐ray analyses, molecular electrostatic potentials, quantum theory of atoms‐in‐molecules, and noncovalent interaction plot analyses show that in crystalline permanganate and perrhenate salts the metal in Mn/ReO4 − anion can act as electron acceptors, the oxygen of another Mn/ReO4 − anion can act as the donor and supramolecular anionic dimers or polymers are formed. The name matere bond (MaB) is proposed to categorize these noncovalent interactions and to differentiate them from the classical metal‐ligand coordination bond.