A Manganese(IV)-Hydroperoxo Intermediate Generated by Protonation of the Corresponding Manganese(III)-Superoxo Complex.

Earlier work revealed that metal-superoxo species primarily function as radicals and/or electrophiles. Herein, we present ambiphilicity of a MnIII-superoxo complex revealed by its proton- and metal-coupled electron-transfer processes. Specifically, a MnIV-hydroperoxo intermediate, [Mn(BDPBrP)(OOH)]+ (1, H2BDPBrP = 2,6-bis((2-(S)-di(4-bromo)phenylhydroxylmethyl-1-pyrrolidinyl)methyl)pyridine) was generated by treatment of a MnIII-superoxo complex, Mn(BDPBrP)(O2•) (2) with trifluoroacetic acid at -120 °C. Detailed insights into the electronic structure of 1 are obtained using resonance Raman and multi-frequency electron paramagnetic resonance spectroscopies coupled with density functional theory calculations. Similarly, the reaction of 2 with scandium(III) triflate was shown to give a Mn(IV)/Sc(III) bridging peroxo species, [Mn(BDPBrP)(OO)Sc(OTf)n](3-n)+ (4). Furthermore, it is found that deprotonation of 1 quantitatively regenerates 2, and that one-electron oxidation of the corresponding MnIII-hydroperoxo species, Mn(BDPBrP)(OOH) (3), also yields 1.

Mononuclear Manganese(III) Superoxo Complexes: Synthesis, Characterization, and Reactivity.

Metal-superoxo species are typically proposed as key intermediates in the catalytic cycle of dioxygen activation by metalloenzymes involving different transition metal cofactors. In this regard, while a series of Fe-, Co-, and Ni-superoxo complexes have been reported to date, well-defined Mn-superoxo complexes remain rather rare. Herein, we report two mononuclear MnIII-superoxo species, Mn(BDPP)(O2•-) (2, H2BDPP = 2,6-bis((2-(S)-diphenylhydroxylmethyl-1-pyrrolidinyl)methyl)pyridine) and Mn(BDPBrP)(O2•-) (2', H2BDPBrP = 2,6-bis((2-(S)-di(4-bromo)phenylhydroxyl-methyl-1-pyrrolidinyl)methyl)pyridine), synthesized by bubbling O2 into solutions of their MnII precursors, Mn(BDPP) (1) and Mn(BDPBrP) (1'), at -80 °C. A combined spectroscopic (resonance Raman and electron paramagnetic resonance (EPR) spectroscopy) and computational study evidence that both complexes contain a high-spin MnIII center (SMn = 2) antiferromagnetically coupled to a superoxo radical ligand (SOO• = 1/2), yielding an overall S = 3/2 ground state. Complexes 2 and 2' were shown to be capable of abstracting a H atom from 2,2,6,6-tetramethyl-1-hydroxypiperidine (TEMPO-H) to form MnIII-hydroperoxo species, Mn(BDPP)(OOH) (5) and Mn(BDPBrP)(OOH) (5'). Complexes 5 and 5' can be independently prepared by the reactions of the isolated MnIII-aqua complexes, [Mn(BDPP)(H2O)]OTf (6) and [Mn(BDPBrP)(H2O)]OTf (6'), with H2O2 in the presence of NEt3. The parallel-mode EPR measurements established a high-spin S = 2 ground state for 5 and 5'.

Conversion of a Fleeting Open-Shell Iron Nitride into an Iron Nitrosyl.

Terminal metal nitrides have been proposed as key intermediates in a series of pivotal chemical transformations. However, exploring the chemical activity of transient tetragonal iron(V) nitrides is largely impeded by their facile dimerization in fluid solutions. Herein, in situ EPR and Mössbauer investigations are presented of unprecedented oxygenation of a paramagnetic iron(V) nitrido intermediate, [FeV N(cyclam-ac)]+ (2, cyclam-ac- =1,4,8,11-tetraazacyclotetradecane-1-acetate anion), yielding an iron nitrosyl complex, [Fe(NO)(cyclam-ac)]+ (3). Further theoretical studies suggest that during the reaction a closed-shell singlet O atom is transferred to 2. Consequently, the N-O bond formation does not follow a radical coupling mechanism proposed for the N-N bond formation but is accomplished by three mutual electron-transfer pathways between 2 and the O atom donor, thanks to the ambiphilic nature of 2.

Lamellar and liquid crystal ordering in solvent-annealed all-conjugated block copolymers.

All-conjugated block copolymers are an emerging class of polymeric materials promising for organic electronic applications, but further progress requires a better understanding of their microstructure including crystallinity and self-assembly through micro-phase segregation. Here, we demonstrate remarkable changes in the thin film structure of a model series of all-conjugated block copolymers with varying processing conditions. Under thermal annealing, poly(3-hexylthiophene)-b-poly(9',9'-dioctylfluorene) (P3HT-b-PF) all-conjugated block copolymers exhibit crystalline features of P3HT or PF, depending on the block ratio, and poor π-π stacking. Under chloroform solvent annealing, the block copolymers exhibit lamellar ordering, as evidenced by multiple reflections in grazing incidence wide- and small-angle X-ray scattering (GIWAXS and GISAXS), including an in-plane reflection indicative of order along the π-π stacking direction for both P3HT and PF blocks. The lamellae have a characteristic domain size of 4.2 nm, and this domain size is found to be independent of block copolymer molecular weight and block ratio. This suggests that lamellar self-assembly arises due to a combination of polymer block segregation and π-π stacking of both P3HT and PF polymer blocks. Strategies for predicting the microstructure of all-conjugated block copolymers must take into account intermolecular π-π stacking and liquid crystalline interactions not typically found in flexible coil block copolymers.

Conjugated block copolymer photovoltaics with near 3% efficiency through microphase separation.

Organic electronic materials have the potential to impact almost every aspect of modern life including how we access information, light our homes, and power personal electronics. Nevertheless, weak intermolecular interactions and disorder at junctions of different organic materials limit the performance and stability of organic interfaces and hence the applicability of organic semiconductors to electronic devices. Here, we demonstrate control of donor-acceptor heterojunctions through microphase-separated conjugated block copolymers. When utilized as the active layer of photovoltaic cells, block copolymer-based devices demonstrate efficient photoconversion well beyond devices composed of homopolymer blends. The 3% block copolymer device efficiencies are achieved without the use of a fullerene acceptor. X-ray scattering results reveal that the remarkable performance of block copolymer solar cells is due to self-assembly into mesoscale lamellar morphologies with primarily face-on crystallite orientations. Conjugated block copolymers thus provide a pathway to enhance performance in excitonic solar cells through control of donor-acceptor interfaces.

Hydrogen Atom Transfer Thermodynamics of Homologous Co(III)- and Mn(III)-Superoxo Complexes: The Effect of the Metal Spin State.

Systematic investigations on H atom transfer (HAT) thermodynamics of metal O2 adducts is of fundamental importance for the design of transition metal catalysts for substrate oxidation and/or oxygenation directly using O2. Such work should help elucidate underlying electronic-structure features that govern the OO-H bond dissociation free energies (BDFEs) of metal-hydroperoxo species, which can be used to quantitatively appraise the HAT activity of the corresponding metal-superoxo complexes. Herein, the BDFEs of two homologous CoIII- and MnIII-hydroperoxo complexes, 3-Co and 3-Mn, were calculated to be 79.3 and 81.5 kcal/mol, respectively, employing the Bordwell relationship based on experimentally determined pK a values and redox potentials of the one-electron-oxidized forms, 4-Co and 4-Mn. To further verify these values, we tested the HAT capability of their superoxo congeners, 2-Co and 2-Mn, toward three different substrates possessing varying O-H BDFEs. Specifically, both metal-superoxo species are capable of activating the O-H bond of 4-oxo-TEMPOH with an O-H BDFE of 68.9 kcal/mol, only 2-Mn is able to abstract a H atom from 2,4-di-tert-butylphenol with an O-H BDFE of 80.9 kcal/mol, and neither of them can react with 3,5-dimethylphenol with an O-H BDFE of 85.6 kcal/mol. Further computational investigations suggested that it is the high spin state of the MnIII center in 3-Mn that renders its OO-H BDFE higher than that of 3-Co, which features a low-spin CoIII center. The present work underscores the role of the metal spin state being as crucial as the oxidation state in modulating BDFEs.

Facile Synthesis of Diamino-Modified Graphene/Polyaniline Semi-Interpenetrating Networks with Practical High Thermoelectric Performance.

p-Phenediamino-modified graphene (PDG) has been newly synthesized via a facile green one-step chemical route as a functionalized graphene-based additive to copolymerize with aniline for fabricating innovative PDG/polyaniline conducting polymer composites containing very special semi-interpenetrating networks (S-IPNs). The S-IPNs not only provide additional pathways by creating chemically bonded PDG and PANI for smoothly transporting carriers but greatly reduce the amount of graphene required to less than a few percent could effectively improve the overall electrical conductivity, Seebeck coefficient, and thus the thermoelectric (TE) performance. The found optimized TE figure of merit (ZT) of 0.74 approaches a practical high level which is comparable or much higher than previously reported ones for TE polymers.

1D copper nanowires for flexible printable electronics and high ampacity wires.

This paper addresses the synthesis and a detailed electrical analysis of individual copper nanowires (CuNWs). One dimensional CuNWs are chemically grown using bromide ions (Br-) as a co-capping agent. By partially replacing alkyl amines with Br-, the isotropic growth on Cu seeds was suppressed during the synthesis. To study the electrical properties of individual CuNWs, a fabrication method is developed which does not require any e-beam lithography process. Chemically grown CuNWs have an ampacity of about 30 million amps per cm2, which is more than one order of magnitude larger than bulk Cu. These good quality, easy to synthesize CuNWs are excellent candidates for creating high ampacity wires and flexible printable electronics.

Molecular Coplanarity and Self-Assembly Promoted by Intramolecular Hydrogen Bonds.

Active conformational control is realized in a conjugated system using intramolecular hydrogen bonds to achieve tailored molecular, supramolecular, and solid-state properties. The hydrogen bonding functionalities are fused to the backbone and precisely preorganized to enforce a fully coplanar conformation of the π-system, leading to short π-π stacking distances, controllable molecular self-assembly, and solid-state growth of one-dimensional nano-/microfibers. This investigation demonstrates the efficiency and significance of an intramolecular noncovalent approach in promoting conformational control and self-assembly of organic molecules.

Thermodynamic synthesis of solution processable ladder polymers.

The synthesis of a carbazole-derived, well-defined ladder polymer was achieved under thermodynamic control by employing reversible ring-closing olefin metathesis. This unique approach featured mild conditions and excellent efficiency, affording the ladder polymer backbone with minimum levels of unreacted defects. Rigorous NMR analysis on a 13C isotope-enriched product revealed that the main-chain contained less than 1% of unreacted precursory vinyl groups. The rigid conformation of the ladder-type backbone was confirmed by photophysical analysis, while the extended rod-like structure was visualized under scanning tunneling microscope. Excellent solubility of this polymer in common organic solvents allowed for feasible processing of thin films using solution-casting techniques. Atomic force microscopy and grazing incident X-ray scattering revealed a uniform and amorphous morphology of these films, in sharp contrast to the polycrystalline thin films of its small molecular counterpart.

Highly Flexible Self-Assembled V2O5 Cathodes Enabled by Conducting Diblock Copolymers.

Mechanically robust battery electrodes are desired for applications in wearable devices, flexible displays, and structural energy and power. In this regard, the challenge is to balance mechanical and electrochemical properties in materials that are inherently brittle. Here, we demonstrate a unique water-based self-assembly approach that incorporates a diblock copolymer bearing electron- and ion-conducting blocks, poly(3-hexylthiophene)-block-poly(ethyleneoxide) (P3HT-b-PEO), with V2O5 to form a flexible, tough, carbon-free hybrid battery cathode. V2O5 is a promising lithium intercalation material, but it remains limited by its poor conductivity and mechanical properties. Our approach leads to a unique electrode structure consisting of interlocking V2O5 layers glued together with micellar aggregates of P3HT-b-PEO, which results in robust mechanical properties, far exceeding the those obtained from conventional fluoropolymer binders. Only 5 wt % polymer is required to triple the flexibility of V2O5, and electrodes comprised of 10 wt % polymer have unusually high toughness (293 kJ/m(3)) and specific energy (530 Wh/kg), both higher than reduced graphene oxide paper electrodes. Furthermore, addition of P3HT-b-PEO enhances lithium-ion diffusion, eliminates cracking during cycling, and boosts cyclability relative to V2O5 alone. These results highlight the importance of tradeoffs between mechanical and electrochemical performance, where polymer content can be used to tune both aspects.

Particle chain display--an optofluidic electronic paper.

A particle-based display medium and a driving mechanism insensitive to the charge polarity of those particles, based on the transformation of particle chains, are developed for reflective electronic paper displays. Particle chains are formed by dipole-dipole interactions between polarized particles with an appropriate electric field applied across the tested display medium, i.e. the solution that regulates the light in the field of display technology, containing neutral polystyrene (PS) particles dispersed in water. Formation of the particle chains results in a large change in optical transmittance and reflectance of the display medium. The performance of the particle chain displays (PCD) was evaluated according to macroscopic (device), microscopic (particle) and optical (reflectance) points of view. A display medium (thickness 100 µm) containing colored PS particles (3 µm, 2.5% w/v) was polarized to display the fixed images of the directly driven electrodes and programmable images of arrayed (5 × 5) electrodes with electric fields (0.48 MV m(-1) and 0.09 MV m(-1), 500 kHz, respectively). The formation of particle chains under electric fields (0.2 MV m(-1) and 0.4 MV m(-1), 500 kHz) was observed in the microscopic images of a display medium (thickness 100 µm) with fluorescent PS particles (5 µm, 1%). Images recorded with a confocal microscope demonstrated the particle chains. The opacity, a common parameter serving to characterize a display medium, was derived by measuring the reflectance ratio of a black background to a white background of the display medium with varied thickness and particle concentration. The temporal response of a display medium (thickness 50 µm) with black PS particles (3 µm, 5%) was tested. When an electric field (0.6 MV m(-1), 500 kHz) was applied, the reflectance increased twice at the first data point in 0.7 s, attaining a contrast ratio of 2. Application of a voltage (20 s) yielded a contrast ratio of 10. The performance of a tested display medium, composed of simple PS particles and water and driven to form particle chains by polarization, is reported.