Evaluation of two- and three-dimensional electrode platforms for the electrochemical characterization of organometallic catalysts incorporated in non-conducting metal-organic frameworks.

The development of a reliable platform for the electrochemical characterization of a redox-active molecular diiron complex, [FeFe], immobilized in a non-conducting metal organic framework (MOF), UiO-66, based on glassy-carbon electrodes is reported. Voltammetric data with appreciable current responses can be obtained by the use of multiwalled carbon nanotubes (MWCNT) or mesoporous carbon (CB) additives that function as conductive scaffolds to interface the MOF crystals in "three-dimensional" electrodes. In the investigated UiO-66-[FeFe] sample, the low abundance of [FeFe] in the MOF and the intrinsic insulating properties of UiO-66 prevent charge transport through the framework, and consequently, only [FeFe] units that are in direct physical contact with the electrode material are electrochemically addressable.

Functional small-molecules & polymers containing P[double bond, length as m-dash]C and As[double bond, length as m-dash]C bonds as hybrid π-conjugated materials.

Stable phospha- and arsaalkenes were used to synthesize polymers containing unsaturated P[double bond, length as m-dash]C and As[double bond, length as m-dash]C moieties. The composition, chemical environment, structure, optical, and electronic properties of the monomers and polymers were elucidated. The incorporation of the heteroatom-carbon double bonded units efficiently perturbs the optoelectronics and solid state features of both monomeric and polymeric scaffolds. Proof-of principle work supports their responsive character through post-functionalisation and electrochromic behaviour. To the best of our knowledge, this is the first example of a polymer containing arsenic-carbon double bonds.

A small electron donor in cobalt complex electrolyte significantly improves efficiency in dye-sensitized solar cells.

Photoelectrochemical approach to solar energy conversion demands a kinetic optimization of various light-induced electron transfer processes. Of great importance are the redox mediator systems accomplishing the electron transfer processes at the semiconductor/electrolyte interface, therefore affecting profoundly the performance of various photoelectrochemical cells. Here, we develop a strategy-by addition of a small organic electron donor, tris(4-methoxyphenyl)amine, into state-of-art cobalt tris(bipyridine) redox electrolyte-to significantly improve the efficiency of dye-sensitized solar cells. The developed solar cells exhibit efficiency of 11.7 and 10.5%, at 0.46 and one-sun illumination, respectively, corresponding to a 26% efficiency improvement compared with the standard electrolyte. Preliminary stability tests showed the solar cell retained 90% of its initial efficiency after 250 h continuous one-sun light soaking. Detailed mechanistic studies reveal the crucial role of the electron transfer cascade processes within the new redox system.

Homogeneous Cobalt/Vanadium Complexes as Precursors for Functionalized Mixed Oxides in Visible-Light-Driven Water Oxidation.

The heterometallic complexes (NH4 )2 [Co(H2 O)6 ]2 [V10 O28 ]⋅4 H2 O (1) and (NH4 )2 [Co(H2 O)5 (ß-HAla)]2 [V10 O28 ]⋅4 H2 O (2) have been synthesized and used for the preparation of mixed oxides as catalysts for water oxidation. Thermal decomposition of 1 and 2 at relatively low temperatures (<500 °C) leads to the formation of the solid mixed oxides CoV2 O6 /V2 O5 (3) and Co2 V2 O7 /V2 O5 (4). The complexes (1, 2) and heterogeneous materials (3, 4) act as catalysts for photoinduced water oxidation. A modification of the thermal decomposition procedure allowed the deposition of mixed metal oxides (MMO) on a mesoporous TiO2 film. The electrodes containing Co/V MMOs in TiO2 films were used for electrocatalytic water oxidation and showed good stability and sustained anodic currents of about 5 mA cm-2 at 1.72 V versus relative hydrogen electrode (RHE). This method of functionalizing TiO2 films with MMOs at relatively low temperatures (<500 °C) can be used to produce other oxides with different functionality for applications in, for example, artificial photosynthesis.

Judicious Ligand Design in Ruthenium Polypyridyl CO2 Reduction Catalysts to Enhance Reactivity by Steric and Electronic Effects.

A series of RuII polypyridyl complexes of the structural design [RuII (R-tpy)(NN)(CH3 CN)]2+ (R-tpy=2,2':6',2''-terpyridine (R=H) or 4,4',4''-tri-tert-butyl-2,2':6',2''-terpyridine (R=tBu); NN=2,2'-bipyridine with methyl substituents in various positions) have been synthesized and analyzed for their ability to function as electrocatalysts for the reduction of CO2 to CO. Detailed electrochemical analyses establish how substitutions at different ring positions of the bipyridine and terpyridine ligands can have profound electronic and, even more importantly, steric effects that determine the complexes' reactivities. Whereas electron-donating groups para to the heteroatoms exhibit the expected electronic effect, with an increase in turnover frequencies at increased overpotential, the introduction of a methyl group at the ortho position of NN imposes drastic steric effects. Two complexes, [RuII (tpy)(6-mbpy)(CH3 CN)]2+ (trans-[3]2+ ; 6-mbpy=6-methyl-2,2'-bipyridine) and [RuII (tBu-tpy)(6-mbpy)(CH3 CN)]2+ (trans-[4]2+ ), in which the methyl group of the 6-mbpy ligand is trans to the CH3 CN ligand, show electrocatalytic CO2 reduction at a previously unreactive oxidation state of the complex. This low overpotential pathway follows an ECE mechanism (electron transfer-chemical reaction-electron transfer), and is a direct result of steric interactions that facilitate CH3 CN ligand dissociation, CO2 coordination, and ultimately catalytic turnover at the first reduction potential of the complexes. All experimental observations are rigorously corroborated by DFT calculations.

Ultrafast and slow charge recombination dynamics of diketopyrrolopyrrole-NiO dye sensitized solar cells.

In a photophysical study, two diketopyrrolopyrrole (DPP)-based sensitizers functionalized with 4-thiophenecarboxylic acid as an anchoring group and a bromo (DPPBr) or dicyanovinyl (DPPCN2) group, and a dyad consisting of a DPP unit linked to a naphthalenediimide group (DPP-NDI), were investigated both in solution and grafted on mesoporous NiO films. Femtosecond transient absorption measurements indicate that ultrafast hole injection occurred predominantly on a timescale of ∼200 fs, whereas the subsequent charge recombination occurred on a surprisingly wide range of timescales, from tens of ps to tens of µs; this kinetic heterogeneity is much greater than is typically observed for dye-sensitized TiO2 or ZnO. Also, in contrast to what is typically observed for dye-sensitized TiO2, there was no significant dependence on the excitation power of the recombination kinetics, which can be explained by the hole density being comparatively higher near the valence band of NiO before excitation. The additional acceptor group in DPP-NDI provided a rapid electron shift and stabilized charge separation up to the µs timescale. This enabled efficient (∼95%) regeneration of NDI by a Co(III)(dtb)3 electrolyte (dtb = 4,4'-di-tert-butyl-2,2'-bipyridine), according to transient absorption measurements. The regeneration of DPPBr and DPPCN2 by Co(III)(dtb)3 was instead inefficient, as most recombination for these dyes occurred on the sub-ns timescale. The transient spectroscopy data thus corroborated the trend of the published photovoltaic properties of dye-sensitized solar cells (DSSCs) based on these dyes on mesoporous NiO, and show the potential of a design strategy with a secondary acceptor bound to the dye. The study identifies rapid initial recombination between the dye and NiO as the main obstacle to obtaining high efficiencies in NiO-based DSSCs; these recombination components may be overlooked when studies are conducted using only methods with ns resolution or slower.

Activating a Low Overpotential CO2 Reduction Mechanism by a Strategic Ligand Modification on a Ruthenium Polypyridyl Catalyst.

The introduction of a simple methyl substituent on the bipyridine ligand of [Ru(tBu3 tpy)(bpy)(NCCH3 )](2+) (tBu3 tpy=4,4',4''-tri-tert-butyl-2,2':6',2''-terpyridine; bpy=2,2'-bipyridine) gives rise to a highly active electrocatalyst for the reduction of CO2 to CO. The methyl group enables CO2 binding already at the one-electron reduced state of the complex to enter a previously not accessible catalytic cycle that operates at the potential of the first reduction. The complex turns over with a Faradaic efficiency close to unity and at an overpotential that is amongst the lowest ever reported for homogenous CO2 reduction catalysts.

The 6,6-dicyanopentafulvene core: a template for the design of electron-acceptor compounds.

The electron-accepting ability of 6,6-dicyanopentafulvenes (DCFs) can be varied extensively through substitution on the five-membered ring. The reduction potentials for a set of 2,3,4,5-tetraphenyl-substituted DCFs, with varying substituents at the para-position of the phenyl rings, strongly correlate with their Hammett σp-parameters. By combining cyclic voltammetry with DFT calculations ((U)B3LYP/6-311+G(d)), using the conductor-like polarizable continuum model (CPCM) for implicit solvation, the absolute reduction potentials of a set of twenty DCFs were reproduced with a mean absolute deviation of 0.10 eV and a maximum deviation of 0.19 eV. Our experimentally investigated DCFs have reduction potentials within 3.67-4.41 eV, however, the computations reveal that DCFs with experimental reduction potentials as high as 5.3 eV could be achieved, higher than that of F4-TCNQ (5.02 eV). Thus, the DCF core is a template that allows variation in the reduction potentials by about 1.6 eV.

2,6-Bis(2,6-diethylphenyliminomethyl)pyridine coordination compounds with cobalt(II), nickel(II), copper(II), and zinc(II): synthesis, spectroscopic characterization, X-ray study and in vitro cytotoxicity.

Coordination compounds with cobalt(II), nickel(II), copper(II) and zinc(II) and the ligand 2,6-bis(2,6-diethylphenyliminomethyl)pyridine (L) were synthesized and fully characterized by IR and UV-Vis-NIR spectroscopy, elemental analysis, magnetic susceptibility and X-ray diffraction for two representative cases. These novel compounds were designed to study their activity as anti-proliferative drugs against different human cancer cell lines. The tridentate ligand forms heptacoordinated compounds from nitrate metallic salts, where the nitrate acts in a chelating form to complete the seven coordination positions. In vitro cell growth inhibition was measured for Co(II), Cu(II) and Zn(II) complexes, as well as for the free ligand. Upon coordination, the IC50 value of the transition-metal compounds is improved compared to the free ligand. The copper(II) and zinc(II) compounds are the most promising candidates for further in vitro and in vivo studies. The activity against colon and prostate cell lines merits further research, in views of the limited therapeutic options for such cancer types.

Redox switching in ethenyl-bridged bisphospholes.

A 2e(-) /2H(+) redox platform has been implemented in the ethenyl-bridged bisphosphol-3-ol 1 to afford the first phospholes that feature chemically reversible oxidations. Oxidation of the title compounds to the corresponding bisphosphol-3-one 2 leads to a change in conjugation topology and a concomitant hypsochromic shift of the lowest-energy absorption maximum by 100 nm. Electrochemical oxidation proceeds without any detectable intermediates, whereas the deprotonated form of 1 can be observed in an aprotic medium during the reduction of 2. This dianionic intermediate 3 is characterized by end absorptions that are bathochromically shifted by circa 200 nm compared to those of 2.

Water oxidation catalyzed by a dinuclear cobalt-polypyridine complex.

The dinuclear Co complex [(TPA)Co(µ-OH)(µ-O2 )Co(TPA)](ClO4 )3 (1, TPA=tris(2-pyridylmethyl)amine) catalyzes the oxidation of water. In the presence of [Ru(bpy)3 ](2+) and S2 O8 (2-) , photoinduced oxygen evolution can be observed with a turnover frequency (TOF) of 1.4±0.1 mol(O2 ) mol(1)(-1) s(-1) and a maximal turnover number (TON) of 58±5 mol(O2 ) mol(1)(-1) . The complex is shown to act as a molecular and homogeneous catalyst and a mechanism is proposed based on the combination of EPR data and light-driven O2 evolution kinetics.

Solvent and pH effects on the redox behavior and catecholase activity of a dicopper complex with distant metal centers.

A dicopper complex is described for which significant catecholase activity was found, particularly for a compound in which the two metal ions are more than 7A apart. Variations on the catecholase activity of this complex were explored in a range of pH values from 5.5 to 9.0 in two solvent mixtures, MeCN/H(2)O and MeOH/H(2)O. The catalytic performance of the complex was found to be substantially better in the second, where the maximum activity was achieved at a pH value one unit lower than in the first. Electrochemical studies of the complex in the absence and presence of dioxygen revealed a very different behavior in each of the two solvent mixtures, which may account for the correspondingly distinct catalytic activity.

Coordination chemistry of a bis(benzimidazole) disulfide: eleven membered chelate ring in cobalt(II), zinc(II) and cadmium(II) halide compounds; oxidative disulfide cleavage when coordinated to nickel(II).

Herein we report the synthesis, structural and spectroscopic characterization of coordination compounds with bis[2-(1H-benzimidazol-2-yl)phenyl]disulfide [bis-(2phSbz)] (1) and cobalt(II), zinc(II) and cadmium(II) halides (2-7). Their X-ray diffraction analyses showed that the metal ions present similar distorted tetrahedral structures, with the disulfide ligand coordinated through the imidazolic nitrogen atoms, forming a twisted eleven membered chelate ring. Structures of nickel(II) compounds 8 and 9, showed that the disulfide bond in the ligand was cleaved forming six membered chelates. In 8, the two ligands are sulfides, however in 9 one of them was oxidized to a sulfone. In both compounds the nickel(II) has a distorted square planar geometry and the sulfur atoms are in cis positions. The oxidation reaction of bis-(2phSbz) was performed in KMnO4/NaOH, giving the 2-(1H,3H-benzimidazolium-2-yl)-benzene sulfonate (10). The solid state structure of compounds 2-5 and 7-10 was determined by X-ray diffraction analyses.

Copper(ii) complexes of a polydentate imidazole-based ligand. pH effect on magnetic coupling and catecholase activity.

A potentially dodecadentate N8O4-donor ligand obtained from 2,2'-biimidazole and l-valine and its tetranuclear Cu(ii) complexes in different degrees of protonation were characterized by chemical and spectroscopic methods. The extensive solution studies performed reveal that the rise in pH media leads successively to the formation of imidazolato (pKa(1) and pKa(2) and hydroxido (pKa(3) and pKa(4)) bridges. A frozen solution EPR study shows a decrease in the signal intensity until an EPR silent spectrum is observed, upon increasing the basicity of the solution. The catalytic performance of the oxidation of 3,5-di-tert-butylcatechol to its corresponding quinone was studied using UV-Vis-NIR absorption spectroscopic methods in CH3CN-H2O and in CH3OH-H2O at pH = 7.5, 8.0 and 8.5. A marked increase in activity, consistent with the formation of the hydroxide bridged species, is observed at pH = 8.5 in both solvent mixtures, but the activity is significantly higher in CH3OH-H2O.

A dicopper complex with distant metal centers. Structure, magnetic properties, electrochemistry and catecholase activity.

The crystal structure and magnetic properties of a dinuclear copper(II) complex of the ligand [2,8-dimethyl-5,11-di-(dimethylethyleneamine) 1,4,5,6,7,10,11,12-octahydroimidazo [4,5-h] imidazo [4,5-c] [1,6]diazecine] dimeim have been investigated. Also, its catecholase activity has been explored in different solvent mixtures: MeCN/H2O and OH/H2O, each at several pH values. In CH3OH/H2O, where the activity was superior, the optimal pH value for the catalytic activity was found to be lower than in CH3CN/H2O. The study of the complex's electrochemical behavior (cyclic voltammetry) which was also investigated in these various media, revealed that although an increase in pH in both solvent mixtures results in an increase both in Me oxidizing power (E(1/2)) and reversibility (ipa/ipc) the change of solvent system seems to be a more influencing factor. The superior catalytic activity found in MeOH/H2O pH=8.0, is associated with a significantly more reversible behavior displayed in this medium. Potentiometric determination of the overall formation constant and three successive pKas for the complex, suggest the formation of stable hydroxo complexes which could be the catalytically active species.