Chameleon Multienvironment Nanoreactors.

Nanoreactors consisting of hydrophilic porous SiO2 shells and amphiphilic copolymer cores have been prepared, which can easily self-tune their hydrophilic/hydrophobic balance depending on the environment and exhibit chameleon-like behavior. The accordingly obtained nanoparticles show excellent colloidal stability in a variety of solvents with different polarity. Most importantly, thanks to the assistance of the nitroxide radicals attached to the amphiphilic copolymers, the synthesized nanoreactors show high catalytic activity for model reactions in both polar and nonpolar environments and, more particularly, realize a high selectivity for the products resulting from the oxidation of benzyl alcohol in toluene.

Tailored Charge Transfer Kinetics in Precursors for Organic Radical Batteries: A Joint Synthetic-Theoretical Approach.

Invited for this month's cover is the group of Stephan Kupfer at the Friedrich Schiller University Jena. The image shows the charge transfer from TEMPO to thiophene in organic radical batteries. The Research Article itself is available at 10.1002/cssc.202201679.

Tailored Charge Transfer Kinetics in Precursors for Organic Radical Batteries: A Joint Synthetic-Theoretical Approach.

The development of sustainable energy storage devices is crucial for the transformation of our energy management. In this scope, organic batteries attracted considerable attention. To overcome the shortcomings of typically applied materials from the classes of redox-active conjugated polymers (i. e., unstable cell voltages) and soft matter-embedded stable organic radicals (i. e., low conductivity), a novel design concept was introduced, integrating such stable radicals within a conductive polymer backbone. In the present theory-driven design approach, redox-active (2,2,6,6-tetramethylpiperidin-1-yl)oxyls (TEMPOs) were incorporated in thiophene-based polymer model systems, while structure-property relationships governing the thermodynamic properties as well as the charge transfer kinetics underlying the charging and discharging processes were investigated in a systematical approach. Thereby, the impact of the substitution pattern, the length as well as the nature of the chemical linker, and the ratio of TEMPO and thiophene units was studied using state-of-the-art quantum chemical and quantum dynamical simulations for a set of six molecular model systems. Finally, two promising candidates were synthesized and electrochemically characterized, paving the way to applications in the frame of novel organic radical batteries.

Hydrophilic Crosslinked TEMPO-Methacrylate Copolymers - a Straight Forward Approach towards Aqueous Semi-Organic Batteries.

Crosslinked hydrophilic poly(2,2,6,6-tetramethylpiperidinyl-N-oxyl-co-[2-(methacryloyloxy)-ethyl]trimethyl ammonium chloride) [poly(TEMPO-co-METAC)] polymers with different monomer ratios are synthesized and characterized regarding a utilization as electrode material in organic batteries. These polymers can be synthesized rapidly utilizing commercial starting materials and reveal an increased hydrophilicity compared to the state-of-the-art poly(2,2,6,6-tetramethylpiperidinyl-N-oxyl-4-methacrylate) (PTMA). By increasing the hydrophilicity of the polymer, a preparation of cathode composites is enabled, which can be used for aqueous semi-organic batteries. Detailed battery testing confirms that the additional METAC groups do not impair the battery behavior while enabling straight-forward zinc-TEMPO batteries.

Synthesis and characterisation of redox hydrogels based on stable nitroxide radicals.

The principle of encapsulation/release of a guest molecule from stimuli responsive hydrogels (SRHs) is mainly realised with pH, temperature or light stimuli. However, only a limited number of redox responsive hydrogels have been investigated so far. We report here the development of a SRH that can release its guest molecule upon a redox stimulus. To obtain this redox hydrogel, we have introduced into the hydrogel the 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) stable nitroxide radical, which can be reversibly oxidized into an oxoammonium cation (TEMPO+). Water solubility is provided by the presence of the (oligoethyleneglycol)methacrylate (OEGMA) comonomer. Electrochemical and mechanical characterization showed that those gels exhibit interesting physicochemical properties, making them very promising candidates for practical use in a wide range of applications.

Sustainable Energy Storage: Recent Trends and Developments toward Fully Organic Batteries.

In times of spreading mobile devices, organic batteries represent a promising approach to replace the well-established lithium-ion technology to fulfill the growing demand for small, flexible, safe, as well as sustainable energy storage solutions. In the last years, large efforts have been made regarding the investigation and development of batteries that use organic active materials since they feature superior properties compared to metal-based, in particular lithium-based, energy-storage systems in terms of flexibility and safety as well as with regard to resource availability and disposal. This Review compiles an overview over the most recent studies on the topic. It focuses on the different types of applied active materials, covering both known systems that are optimized and novel structures that aim at being established.

An Approach Toward Replacing Vanadium: A Single Organic Molecule for the Anode and Cathode of an Aqueous Redox-Flow Battery.

By combining a viologen unit and a 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) radical in one single combi-molecule, an artificial bipolar redox-active material, 1-(4-(((1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)oxy)carbonyl)benzyl)-1'-methyl-[4,4'-bipyridine]-1,1'-diium-chloride (VIOTEMP), was created that can serve as both the anode (-0.49 V) and cathode (0.67 V vs. Ag/AgCl) in a water-based redox-flow battery. While it mimics the redox states of flow battery metals like vanadium, the novel aqueous electrolyte does not require strongly acidic media and is best operated at pH 4. The electrochemical properties of VIOTEMP were investigated by using cyclic voltammetry, rotating disc electrode experiments, and spectroelectrochemical methods. A redox-flow battery was built and the suitability of the material for both electrodes was demonstrated through a polarity-inversion experiment. Thus, an organic aqueous electrolyte system being safe in case of cross contamination is presented.

High-Power-Density Organic Radical Batteries.

Batteries that are based on organic radical compounds possess superior charging times and discharging power capability in comparison to established electrochemical energy-storage technologies. They do not rely on metals and, hence, feature a favorable environmental impact. They furthermore offer the possibility of roll-to-roll processing through the use of different printing techniques, which enables the cost-efficient fabrication of mechanically flexible devices. In this review, organic radical batteries are presented with the focus on the hitherto developed materials and the key properties thereof, e.g., voltage, capacity, and cycle life. Furthermore, basic information, such as significant characteristics, housing approaches, and applied additives, are presented and discussed in the context of organic radical batteries.

Soluble PtII-Containing Polymers Based on a 2,6-Bis(1H-1,2,3-triazol-4-yl)-4-ethynylpyridine Ligand.

A soluble PtII-acetylide polymer 6 was prepared in a supramolecular polymerization of a PtII-chloro precursor complex 5, which represents a self-complementary AB-type monomer. This new type of polymer combines the structural features of the common polyplatinynes and cationic PtII-acetylide complexes. Though the photophysical and electrochemical properties of the material still need to be advanced, a versatile and straightforward method for the preparation of soluble, cationic PtII-acetylide polymers with phosphorescent behavior is offered.

Polymer-Based Organic Batteries.

The storage of electric energy is of ever growing importance for our modern, technology-based society, and novel battery systems are in the focus of research. The substitution of conventional metals as redox-active material by organic materials offers a promising alternative for the next generation of rechargeable batteries since these organic batteries are excelling in charging speed and cycling stability. This review provides a comprehensive overview of these systems and discusses the numerous classes of organic, polymer-based active materials as well as auxiliary components of the battery, like additives or electrolytes. Moreover, a definition of important cell characteristics and an introduction to selected characterization techniques is provided, completed by the discussion of potential socio-economic impacts.

Efficient Energy Transfer and Metal Coupling in Cyanide-Bridged Heterodinuclear Complexes Based on (Bipyridine)(terpyridine)ruthenium(II) and (Phenylpyridine)iridium(III) Complexes.

We report a series of cyanide-bridged, heterodinuclear iridium(III)-ruthenium(II) complexes with the generalized formula [Ir((R2)2-ppy)2(CN)(µ-CN)Ru(bpy)(tpy-R1)]PF6 (ppy = 2-phenylpyridine, bpy = 2,2'-bipyridine, and tpy = 2,2':6',2″-terpyridine). The structural, spectroscopic, and electrochemical properties were analyzed in the context of variation of the electron-withdrawing (e.g., -F, -Br, -CHO) and -donating (e.g., -Me) and extended π-conjugated groups at several positions. In total, ten dinuclear complexes and the appropriate model complexes have been prepared. The iridium(III)-based emission is almost fully quenched in these complexes, and only the ruthenium(II)-based emission is observed, which indicates an efficient energy transfer toward the Ru center. Upon oxidation of the Ru center, the fluorinated complexes 2 exhibit a broad intervalence charge-transfer transition in the near-infrared region. The complexes are assigned to a weakly coupled class II system according to the Robin-Day classification. The electronic structure was evaluated by density functional theory (DFT) and time-dependent DFT calculations to corroborate the experimental data.

An aqueous, polymer-based redox-flow battery using non-corrosive, safe, and low-cost materials.

For renewable energy sources such as solar, wind, and hydroelectric to be effectively used in the grid of the future, flexible and scalable energy-storage solutions are necessary to mitigate output fluctuations. Redox-flow batteries (RFBs) were first built in the 1940s and are considered a promising large-scale energy-storage technology. A limited number of redox-active materials--mainly metal salts, corrosive halogens, and low-molar-mass organic compounds--have been investigated as active materials, and only a few membrane materials, such as Nafion, have been considered for RFBs. However, for systems that are intended for both domestic and large-scale use, safety and cost must be taken into account as well as energy density and capacity, particularly regarding long-term access to metal resources, which places limits on the lithium-ion-based and vanadium-based RFB development. Here we describe an affordable, safe, and scalable battery system, which uses organic polymers as the charge-storage material in combination with inexpensive dialysis membranes, which separate the anode and the cathode by the retention of the non-metallic, active (macro-molecular) species, and an aqueous sodium chloride solution as the electrolyte. This water- and polymer-based RFB has an energy density of 10 watt hours per litre, current densities of up to 100 milliamperes per square centimetre, and stable long-term cycling capability. The polymer-based RFB we present uses an environmentally benign sodium chloride solution and cheap, commercially available filter membranes instead of highly corrosive acid electrolytes and expensive membrane materials.

New ruthenium bis(terpyridine) methanofullerene and pyrrolidinofullerene complexes: synthesis and electrochemical and photophysical properties.

A series of terpyridine (tpy) methanofullerene and pyrrolidinofullerene dyads linked via p-phenylene or p-phenyleneethynylenephenylene (PEP) units is presented. The coordination to ruthenium(II) yields donor-bridge-acceptor assemblies with different lengths. Cyclic voltammetry and UV-vis and luminescence spectroscopy are applied to study the electronic interactions between the active moieties. It is shown that, upon light excitation of the ruthenium(II)-based (1)MLCT transition, the formed (3)MLCT state is readily quenched in the presence of C60. The photoinduced dynamics have been studied by transient absorption spectroscopy, which reveals fast depopulation of the (3)MLCT (73-406 ps). As a consequence, energy transfer occurs, populating a long-lived triplet state, which could be assigned to the (3)C60* state.

Anion receptors based on halogen bonding with halo-1,2,3-triazoliums.

A systematic series of anion receptors based on bidentate halogen bonding by halo-triazoles and -triazoliums is presented. The influence of the halogen bond donor atom, the electron-withdrawing group, and the linker group that bridges the two donor moieties is investigated. Additionally, a comparison with hydrogen bond-based analogues is provided. A new, efficient synthetic approach to introduce different halogens into the heterocycles is established using silver(I)-triazolylidenes, which are converted to the corresponding halo-1,2,3-triazoliums with different halogens. Comprehensive nuclear magnetic resonance binding studies supported by isothermal titration calorimetry studies were performed with different halides and oxo-anions to evaluate the influence of key parameters of the halogen bond donor, namely, polarization of the halogen and the bond angle to the anion. The results show a larger anion affinity in the case of more charge-dense halides as well as a general preference of the receptors to bind oxo-anions, in particular sulfate, over halides.

Dithiophenedione-containing polymers for battery application.

Redox-active polymers have received recently significant interest as active materials in secondary organic batteries. We designed a redox-active monomer, namely 2-vinyl-4,8-dihydrobenzo[1,2-b:4,5-b']dithiophene-4,8-dione that exhibits two one-electron redox reactions and has a low molar mass, resulting in a high theoretical capacity of 217 mAh/g. The free radical polymerization of the monomer was optimized by variation of solvent and initiator. The electrochemical behavior of the obtained polymer was investigated using cyclic voltammetry. The utilization of lithium salts in the supporting electrolyte leads to a merging of the redox waves accompanied by a shift to higher redox potentials. Prototype batteries manufactured with 10 wt % polymer as active material exhibit full material activity at the first charge/discharge cycle. During the first 100 cycles, the capacity drops to 50%. Higher contents of polymer (up to 40 wt %) leads to a lower material activity. Furthermore, the battery system reveals a fast charge/discharge ability, allowing a maximum speed up to 10C (6 min) with only a negligible loss of capacity.

Poly(exTTF): a novel redox-active polymer as active material for li-organic batteries.

The first polymer bearing exTTF units intended for the use in electrical charge storage is presented. The polymer undergoes a redox reaction involving two electrons at -0.20 V vs Fc/Fc(+) and is applied as active cathode material in a Li-organic battery. The received coin cells feature a theoretical capacity of 132 mAh g(-1) , a cell potential of 3.5 V, and a lifetime exceeding more than 250 cycles.

Physicochemical analysis of ruthenium(II) sensitizers of 1,2,3-triazole-derived mesoionic carbene and cyclometalating ligands.

A series of heteroleptic bis(tridentate) ruthenium(II) complexes bearing ligands featuring 1,2,3-triazolide and 1,2,3-triazolylidene units are presented. The synthesis of the C^N^N-coordinated ruthenium(II) triazolide complex is achieved by direct C-H activation, which is enabled by the use of a 1,5-disubstituted triazole. By postcomplexation alkylation, the ruthenium(II) 1,2,3-triazolide complex can be converted to the corresponding 1,2,3-triazolylidene complex. Additionally, a ruthenium(II) complex featuring a C^N^C-coordinating bis(1,2,3-triazolylidene)pyridine ligand is prepared via transmetalation from a silver(I) triazolylidene precursor. The electronic consequences of the carbanion and mesoionic carbene donors are studied both experimentally and computationally. The presented complexes exhibit a broad absorption in the visible region as well as long lifetimes of the charge-separated excited state suggesting their application in photoredox catalysis and photovoltaics. Testing of the dyes in a conventional dye-sensitized solar cell (DSSC) generates, however, only modest power conversion efficiencies (PCEs).

Synthesis and characterization of poly(phenylacetylene)s with Ru(II) bis-terpyridine complexes in the side-chain.

An alkyne-functionalized ruthenium(II) bis-terpyridine complex is directly copolymerized with phenylacetylene by alkyne polymerization. The polymer is characterized by size-exclusion chromatography (SEC), (1) H NMR spectroscopy, cyclic voltammetry (CV) measurements, and thermal analysis. The photophysical properties of the polymer are studied by UV-vis absorption spectroscopy. In addition, spectro-electrochemical measurements are carried out. Time-resolved luminescence lifetime decay curves show an enhanced lifetime of the metal complex attached to the conjugated polymer backbone compared with the Ru(tpy)2 (2+) model complex.

Designing cyclometalated ruthenium(II) complexes for anodic electropolymerization.

The anodic electropolymerization of thiophene-functionalized cyclometalated ruthenium(II) complexes is shown for the first time. Oxidative decomposition reactions can be overcome by modification of the involved redox potentials through the introduction of electron-withdrawing substituents, namely nitro groups, at the cyclometalating phenyl ring. The generated functionalized ruthenium(II) complexes allow the electrochemical preparation of thin polymer films, which show a broad UV/Vis absorption as well as reversible redox switchability. The presented complexes are promising candidates for future photovoltaic applications based on photo-redox-active films.

A heteroleptic bis(tridentate) ruthenium(II) platform featuring an anionic 1,2,3-triazolate-based ligand for application in the dye-sensitized solar cell.

A series of bis(tridentate) ruthenium(II) complexes featuring new anionic 1,2,3-triazolate-based tridentate ligands and 2,2':6',2''-terpyridine is presented. For a complex equipped with carboxy anchoring groups, the performance in a dye-sensitized solar cell is evaluated. The title complexes are readily synthesized and can be decorated with alkyl chains utilizing azide-alkyne cycloaddition methods, in order to improve the device stability and allow the use of alternative electrolytes. On account of the strong electron donation from the 1,2,3-triazolates, the complexes exhibit a broad metal-to-ligand charge-transfer absorption (up to 700 nm), leading to an electron transfer toward the anchoring ligand. The lifetimes of the charge-separated excited states are in the range of 50 to 80 ns. In addition, the ground- and excited-state redox potentials are appropriate for the application in dye-sensitized solar cells, as demonstrated by power conversion efficiencies of up to 4.9% (vs 6.1% for N749).