Stable Radical Isoporphyrin Copolymer Prepared with Di(phenylphosphane).

Two diphosphanes with variable-length ligands tested as nucleophiles to prepare isoporphyrin copolymers in the presence of ditolylporphyrin of zinc (ZnTP) prevented the oxidation of the diphosphine ligand. This paper demonstrates the power of this approach and describes the photoelectrocatalytic properties. The obtained copolymers were characterized by UV-vis spectroscopy, X-ray photoelectron spectroscopy, atomic force micrograph (AFM), EQCM (Electrochemical Quartz Cristal Microbalance) and electrochemistry.

Synthesis, Characterization, and Properties of a Titanium(IV)-Tetrathiafulvalene-Based Complex.

To deeply investigate the interaction between a tetrathiafulvalene (TTF) unit and a Ti(IV) center, a monomeric heteroleptic octahedral Ti(IV) complex containing a diimine ligand composed of a 1,10-phenanthroline core fused with a TTF fragment (ligand ) was prepared. The stable complex formulated as Ti()(), where is a 2,2'-biphenolato derivative, was efficiently synthesized by following a one-step approach. This complex and its model species [Ti()()] were fully characterized in solution, and their solid-state structures were established by single-crystal X-ray diffraction analysis.

Syntheses and Electrochemical and EPR Studies of Porphyrins Functionalized with Bulky Aromatic Amine Donors.

A series of nickel(II) porphyrins bearing one or two bulky nitrogen donors at the positions were prepared by using Ullmann methodology or more classical Buchwald-Hartwig amination reactions to create the new C-N bonds. For several new compounds, single crystals were obtained, and the X-ray structures were solved. The electrochemical data of these compounds are reported.

Proton-Conductive Supramolecular Hydrogen-Bonded Organic Superstructures for High-Performance Zinc-Organic Batteries.

With fast (de)coordination kinetics, the smallest and the lightest proton stands out as the most ideal charge carrier for aqueous Zn-organic batteries (ZOBs). Hydrogen-bonding networks with rapid Grotthuss proton conduction is particularly suitable for organic cathodes, yet not reported. We report the supramolecular self-assembly of cyanuric acid and 1,3,5-triazine-2,4,6-triamine into organic superstructures through in-plane H-bonds and out-of-plane π-π interaction.

Anionic Co-insertion Charge Storage in Dinitrobenzene Cathodes for High-Performance Aqueous Zinc-Organic Batteries.

Highly active and stable cathodes are critical for aqueous Zn-organic batteries with high capacity, fast redox kinetics, and long life. We herein report para-, meta-, and ortho-dinitrobenzene (p-, m-, and o-DB) containing two successive two-electron processes, as cathode materials to boost the battery performance. Theoretical and experimental studies reveal that nitro constitutional isomerism is key to zincophilic activity and redox kinetics.

Self-Assembled Carbon Superstructures Achieving Ultra-Stable and Fast Proton-Coupled Charge Storage Kinetics.

Designing ingenious and stable carbon nanostructures is critical but still challenging for use in energy storage devices with superior electrochemistry kinetics, durable capacitive activity, and high rate survivability. To pursue the objective, a simple self-assembly strategy is developed to access carbon superstructures built of nanoparticle embedded plates. The carbon precursors, 2,4,6-trichloro-1,3,5-triazine and 2,6-diaminoanthraquinone can form porous organic polymer with "protic salt"-type rigid skeleton linked by -NH Cl - "rivets", which provides the cornerstone for hydrogen-bonding-guided self-assembly of the organic backbone to superstructures by π-π plane stacking.

Porphyrins and Polyoxometalate Scaffolds.

Polyoxometalates (POMs) can act as unique reservoirs for multiple electron transfers. As POMs display only weak absorption in the visible spectrum, they can be associated with chromophores such as porphyrins and porphyrin antennae. In this Minireview, the research dedicated to the combination of porphyrins and polyoxometalates is put in context and the state of the art identifying the challenges addressed in the optimization of hybrid materials for applications is detailed.

Ni -Containing 54-Tungsto-6-Silicate: Synthesis, Structure, Magnetic and Electrochemical Studies.

The 36-Ni -containing 54-tungsto-6-silicate, [Ni (OH) (H O) (SiW O ) ] (Ni ) was synthesized by a simple one-pot reaction of the Ni -pivalate complex [Ni (μ-OH )(O CCMe ) (HO CCMe ) ] with the trilacunary [SiW O ] polyanion precursor in water and structurally characterized by a multitude of physicochemical techniques including single-crystal XRD, FTIR, TGA, elemental analysis, magnetic and electrochemical studies. Polyanion Ni comprises six equivalent {Ni SiW } units which are linked by Ni-O-W bridges forming a macrocyclic assembly. Magnetic studies demonstrate that the {Ni } building blocks in Ni remain magnetically intact while forming a hexagonal ring with antiferromagnetic exchange interactions between adjacent {Ni } units.

Enhancement of photocurrent by incorporation of Preyssler type polyoxometalate protected nanoparticles in polyporphyrin films.

The introduction of nanoparticles (MNPs) at the surface of cationic poly-porphyrin films, obtained by electrostatic interaction between the bis-porphyrin copolymer and the Preyssler type polyoxometalate P5W30@MNPs, enhances the photocurrent (up to 2.5-3 times greater as a function of the used nanoparticle).

An Efficient Electrochromic Supercapacitor Based on Solution-Processable Nanoporous Poly{tris[4-(3,4-ethylenedioxythiophene)phenyl]amine}.

A new green synthetic route to tris[4-(3,4-ethylenedioxythiophene)phenyl]amine (TEPA) monomer has been developed and the molecular structure of TEPA has been determined by using single-crystal XRD. Solution-processable nanoporous poly{tris[4-(3,4-ethylenedioxythiophene)phenyl]amine} (PTEPA) is prepared by a chemical oxidative polymerization in a microemulsion. Based on the distorted structure of TEPA in the solid state, it is proposed that dendritic PTEPA has a distorted 3 D conformation with multiple twisted channels and pores that are narrowed and blocked by bifurcation and distortion of PTEPA, which is consistent with the observed hierarchical pore structure.

Recycling Iron-Containing Sludges from the Electroflocculation of Printing and Dyeing Wastewater into Anode Materials for Lithium-Ion Batteries.

Iron-containing sludges (DW/Fe) were prepared by the electroflocculation of industrial printing and dyeing wastewater (DW). To investigate the formation process and the properties of the DW/Fe sludges and their application in anode materials in Li-ion batteries, the DW/Fe sludges were compared to three other sludges (MB/Fe, RB/Fe, Ta/Fe) prepared from model solutions that contained either methyl blue (MB), rhodamine B (RB), or tartrazine (Ta). The DW/Fe sludges were calcined at 500 °C under N to form iron oxide/carbon composite C-DW/Fe.

Polyoxovanadate-iodobodipy supramolecular assemblies: new agents for high efficiency cancer photochemotherapy.

Two novel polyoxovanadate-iodoBodipy supramolecular assemblies, named as (2I-BDP-C6)2V6 and (2I-BDP-C6)3V10, were first synthesized by the self-assembly of anionic hexavanadate and decavanadate with cationic iodoBodipy for photochemotherapy, respectively. The mechanisms for synergistic photochemotherapy of the anion-cation pairs were determined. In particular, (2I-BDP-C6)3V10 can effectively kill lung cancer cells (HepG2) by synergetic chemotherapy as well as photodynamic therapy.

Synthesis of new Mn analogues and their structural, electrochemical and catalytic properties.

We report the synthesis and structural characterisation of new Mn19 and Mn18M analogues, [MnIII12MnII7(μ4-O)8(μ3-OCH3)2(μ3-Br)6(HLMe)12(MeOH)6]Br2 (2) and [MnIII12MnII6Sr(μ4-O8(μ3-Cl)8(HLMe)12(MeCN)6]Cl2 cluster (3), where H3LMe is 2,6-bis(hydroxymethyl)-p-cresol. The electrochemistry of 2 and 3 has been investigated and their activity as catalysts in the oxidation of benzyl alcohol has been evaluated. Selective oxidation of benzyl alcohol to benzaldehyde by O2 was achieved using 1 mol% of catalyst with conversions of 74% (2) and 60% (3) at 140 °C using TEMPO as a co-catalyst.

A Highly Stable Organic Radical Cation.

Functionalization of a methylviologen with four methyl ester substituents significantly facilitates the first two reduction steps. The easily generated radical cation shows markedly improved air stability compared to the parent methylviologen, making this derivative of interest in organic electronic applications.

Conjugated hybrid films based on a new polyoxotitanate monomer.

Electropolymerisation of the novel polyoxotitanate (POT) hexamer [Ti(μ3-O)(OiPr)(TA)]6 (TA = thiophene-3-acetate) with 3,4-ethylenedioxythiophene (EDOT) gives films of hybrid conjugated copolymer, Poly-(EDOT-POT)s, the morphologies of which are, uniquely, influenced by the electropolymerisation potential. Nanoporous Poly-(EDOT-POT)-1 is a fast-ion electrode material and has improved electrochromic properties and significantly higher capacitance than that of the parent poly(3,4-ethylenedioxythiophene) (PEDOT).

Anderson-Type Polyoxometalates Functionalized by Tetrathiafulvalene Groups: Synthesis, Electrochemical Studies, and NLO Properties.

Three polyoxometalates (POMs) functionalized by tetrathiafulvalene (TTF) molecules have been synthesized by a coupling reaction between the Anderson-type POMs [MnMoO{(OCH)CNH}] or [AlMoO(OH){(OCH)CNH}] and the TTF carboxylic acid derivative (MeS)TTF(S-CH-COH). The monofunctionalized TTF-AlMo POM contains one TTF group covalently grafted on an Al Anderson platform. The symmetrical TTF-MnMo-TTF POM possesses two TTF groups grafted on each side of a Mn Anderson derivative while the asymmetrical TTF-MnMo-SP POM contains a TTF and a spiropyran groups.

Photoredox-Switchable Resorcin[4]arene Cavitands: Radical Control of Molecular Gripping Machinery via Hydrogen Bonding.

Semiquinones (SQ) are generated in photosynthetic organisms upon photoinduced electron transfer to quinones (Q). They are stabilized by hydrogen bonding (HB) with the neighboring residues, which alters the properties of the reaction center. We designed, synthesized, and investigated resorcin[4]arene cavitands inspired by this function of SQ in natural photosynthesis.

A Four-Step Synthesis of Substituted 5,11-Dicyano-6,12-diaryltetracenes with Enhanced Stability and High Fluorescence Emission.

A four-step synthesis of substituted 5,11-dicyano-6,12-diaryltetracenes was developed, starting from readily available para-substituted benzophenones. The key step of this straightforward route is the complex cascade reaction between tetraaryl[3]cumulenes and tetracyanoethene (TCNE) resulting in 5,5,11,11-tetracyano-5,11-dihydrotetracenes. The mechanism of this transformation was reinvestigated by means of theoretical calculations.

Porphyrin Donor and Tunable Push-Pull Acceptor Conjugates-Experimental Investigation of Marcus Theory.

We report on a series of electron donor-acceptor conjugates incorporating a Zn -porphyrin-based electron donor and a variety of non-conjugated rigid linkers connecting to push-pull chromophores as electron acceptors. The electron acceptors comprize multicyanobutadienes or extended tetracyanoquinodimethane analogues with first reduction potentials ranging from -1.67 to -0.

N-Heterocyclic Carbene Based Tri-organyl-Zn-Alkyl Cations: Synthesis, Structures, and Use in CO Functionalization.

Tri-organyl and tricoordinate N-heterocyclic carbene (NHC) Zn-NHC alkyl cations [(nNHC) Zn-Me] (nNHC=C2-bonded-IMes/-IDipp; 3 and 4 ; IMes=1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene, IDipp=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) were first synthesized and structurally characterized by ionization of the corresponding neutral precursors [(nNHC)ZnMe ] with [Ph C][B(C F ) ] in the presence of one equivalent of free NHC. Whereas cation [(nIMes) Zn-Me] (3 ) is stable, its sterically congested analogue [(nIDipp) Zn-Me] (4 ) readily undergoes an nNHC-to-aNHC isomerization in the presence of THF or IDipp to afford the more thermodynamically stable [(aIDipp)(nIDipp)Zn-Me] (aIDipp=C4-bonded IDipp, 5 ), reflecting the adaptable-to-sterics coordination chemistry of these cations for improved stability. Cations 3 -5 are the first Zn cations of the type Zn(C)(C')(C'') (C, C', C''=σ-donor carbyl ligand).

Flexible Viologen Cyclophanes: Odd/Even Effects on Intramolecular Interactions.

The ability of three bis-viologen cyclophanes to act as redox-triggered contractile switches is investigated. Odd/even effects in the formation of cyclic bis-viologens are circumvented by the use of a Zincke salt intermediate and a tetrathiafulvalene template to prepare a flexible cyclophane with hexyl linkers. Comparative spectro-electrochemical studies of this macrocycle with two other pentyl- or heptyl-linked cyclic bis-viologens show that the development of intramolecular interactions in aqueous solution depends on the length of the bridges.