Tris Cobalt Research Articles

Strong Enhancement in Cobalt(II)‐TPMA Aqueous Hydrogen Photosynthesis through Intramolecular Proton Relay

AbstractPhotosynthetic hydrogen generation by cobalt(II) tris(2‐pyridylmethyl)amine (TPMA) complexes is mainly limited by protonation kinetics and decomposition routes involving demetallation. In the present work we have explored the effects of both proton shuttles and improved rigidity on the catalytic ability of cobalt(II) TPMA complexes. Remarkably, we demonstrate that, while a small enhancement in the catalytic performance is attained in a rigid cage structure, the introduction of ammonium groups as proton transfer relays in close proximity to the cobalt center allows to reach a 4‐fold increase in the quantum efficiency of H2 formation, and a surprising 22‐fold gain in the maximum turnover number, at low catalyst concentration. The beneficial role of the ammonium relays in promoting faster intramolecular proton transfer to the reduced cobalt center is documented by transient absorption spectroscopy, showcasing the great relevance of tuning the catalyst periphery to achieve efficient catalysis of solar fuel formation.

Strong Enhancement in Cobalt(II)-TPMA Aqueous Hydrogen Photosynthesis through Intramolecular Proton Relay.

Photosynthetic hydrogen generation by cobalt(II) tris(2-pyridylmethyl)amine (TPMA) complexes is mainly limited by protonation kinetics and decomposition routes involving demetallation. In the present work we have explored the effects of both proton shuttles and improved rigidity on the catalytic ability of cobalt(II) TPMA complexes. Remarkably, we demonstrate that, while a small enhancement in the catalytic performance is attained in a rigid cage structure, the introduction of ammonium groups as proton transfer relays in close proximity to the cobalt center allows to reach a 4-fold increase in the quantum efficiency of H2 formation, and a surprising 22-fold gain in the maximum turnover number, at low catalyst concentration. The beneficial role of the ammonium relays in promoting faster intramolecular proton transfer to the reduced cobalt center is documented by transient absorption spectroscopy, showcasing the great relevance of tuning the catalyst periphery to achieve efficient catalysis of solar fuel formation.

A cobalt templated outer sphere hydrogen bond donor catalyst derived from 2-guanidinobenzimidazole: Synthesis, applications in carbon–carbon bond forming reactions, structure

A lipophilic tricationic cobalt tris(chelate) complex of 2-guanidinobenzimidazole (GBI), [Co(GBI)3]3+ 3BArf– (23+ 3BArf–; BArf = B(3,5-C6H3(CF3)2)4), is prepared from the corresponding hydrophilic trichloride salt and Na+ BArf– or Ag+ BArf– under aqueous/organic biphasic conditions. This racemic chiral complex, which is obtained as a mer isomer and a tetradecahydrate as assayed by NMR and TGA, is an excellent catalyst for additions of dimethyl malonate and indole to trans-ß-nitrostyrenes (10 mol%), and cycloadditions of CO2 to epoxides (1 mol%; solvent-free). Average yields (84 %, 91 %, 81 %) and rates are slightly greater than those obtained with a monocationic ruthenium GBI complex [(η5-C5H5)Ru(CO)(GBI)]+ BArf– prepared earlier. Attempted crystallization of 23+ 3Cl– gives a tetramethanol solvate of a salt derived from loss of two molecules of HCl. This can be represented as [Co(GBI)(GBI–H)2]+ Cl−, and bond lengths and hydrogen bonding motifs are carefully analyzed, especially in the context of dominant chelate resonance forms.

Doping Strategies for Tetrasubstituted Paracyclophane Hole Transport Layers in Perovskite Solar Cells

AbstractBecause of its excellent hole conductivity, p‐doped 2,2′7,7′‐tetrakis‐(N,N‐di‐p‐methoxyphenyl‐amine)‐9,9′‐spiro‐bifluorene (spiro‐MeOTAD) is commonly deployed for hole transport in organic metal halide perovskite solar cells, but its rather expensive synthesis prompts the research for alternatives. In this work, tetrasubstituted [2.2]paracyclophanes (PCPs) are synthesized and investigated for replacing spiro‐MeOTAD. To enhance their conductivity, different doping strategies are followed. Best conductivities are achieved by doping PCP thin films with tris(2‐(1H‐pyrazol‐1‐yl)‐4‐tert‐butylpyridine)cobalt(III) tris(bis(trifluoromethylsulfonyl)imide) (FK209), matching the conductivity of state‐of‐the‐art p‐doped spiro‐MeOTAD. Best performance in solar cells is leveraged by doping PCPs with the co‐dopants lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and 4‐tert‐butylpyridine (tBP) which are also used to p‐dope spiro‐MeOTAD thin films in solar cells. Yet, the thermal device stability is maximized upon doping PCPs with FK209 and 2,3,5,6‐tetrafluoro‐7,7,8,8‐tetracyanoquinodimethane (F4TCNQ).

Effect of symmetry and substituents of cobalt based phthalocyanines in aptasensor design for the electrochemical impedimetric detection of the human epidermal growth factor receptor 2

Surface functionalization in biosensor design remains the major contributor to biosensor efficiency and selectivity. In electrochemical biosensor design, the surface is usually functionalized to achieve immobilization of the biorecognition element as well as electron transfer mediation for signal amplification. An asymmetric cobalt tris-(acetylphenoxy)-mono-phenoxyacrylic acid phthalocyanine (CoMPhAaPc) and a symmetric cobalt tetra-acetylphenoxy phthalocyanine were used for immobilization of HB5 aptamer and signal amplification towards the electrochemical detection of the human epidermal growth factor 2 (HER2). The efficiency of the two phthalocyanines is compared in relation to the substituents and symmetry. The two phthalocyanines were further coupled with sulphur nitrogen graphene quantum dots (SNGQDs) via π-π interactions, for enhanced activity and performance towards HER2 detection. The efficiency of the designed sensors was tested using the detection of HER2 in human serum. The best performance was observed for the SNGQDs(π)CoMPhAaPc/HB5 (amide) with limit of detection value of 0.0027 ng/mL and sensitivity of 72,253 Ωng−1mL. Considering these results, the aptasensors demonstrate great potential for improved monitoring of human epidermal growth factor receptor 2 levels for the management of breast cancer.

Cobalt tris(4-vinylphenyl)corrole: out of the frying pan into the polymer.

A novel cobalt corrole bearing 4-vinylphenyl groups at the 5,10,15-meso-positions of the macrocycle has been synthesized from tris(4-bromophenyl)corrole using a Suzuki coupling reaction. The spectral and electrochemical properties are reported in CH2Cl2 along with its ability to form a highly stable six-coordinate complex and cross-linked corrole-based polymer in a 59% yield.

Photocatalytic CO2 reduction by a Z-scheme mechanism in an aqueous suspension of particulate (CuGa)0.3Zn1.4S2, BiVO4 and a Co complex operating dual-functionally as an electron mediator and as a cocatalyst

A visible-light-driven Z-scheme photocatalytic CO2 reduction reaction (CO2RR) to produce CO was demonstrated using an aqueous particulate dispersion containing two bare semiconductors, (CuGa)0.3Zn1.4S2 for CO2RR and BiVO4 for water oxidation. The semiconductors were mixed with a water-soluble cobalt tris(dimethylbipyridine) complex. The CO selectivity was 98% (against H2), and the rate of CO generation was 1–2 orders of magnitude higher than those of previously-reported aqueous suspension photocatalytic systems. O2 was continuously evolved, and isotope tracer analyses confirmed that CO2 was the carbon source for CO. Experimental studies and calculations suggest that the Co complex acts dual-functionally in synergy with (CuGa)0.3Zn1.4S2 and BiVO4: it behaves as an efficient ionic electron mediator, and also acts as a new active CO2RR cocatalyst after a structural change by accepting photoexcited electrons from (CuGa)0.3Zn1.4S2. This simple method, operating in a self-optimizing manner in solution, has great potential to help achieve sustainable, highly active artificial photosynthetic systems.

Systematic Study of Perovskite Layers if Doped with Strong Oxidants

Herein, strong oxidants are employed for the first time to stabilize the main frame structure of the perovskite [PbI6]4− by strengthening the interaction between the central Pb atom and coordination I atoms. A systematic study on the microstructure and macrostate of the perovskite is carried out by the synchrotron radiation technique and conventional characterization. According to the valence state and local environment of each chemical element, crystallinity and morphology of the active layer, and photoelectric properties of the solar cell, the strong oxidants, tris[2‐((1H‐pyrazol‐1‐yl)‐4‐tert‐butylpyridine)cobalt(III)tris(bis(trifluoromethylsulfonyl)imide)] (FK209) and Na2S2O8, can increase the power conversion efficiency and stability of the doped devices. A possible mechanism of doping strong oxidants is explained.

An X-ray investigation of stereoselectivity in the interactions of [Co(en)3]3+ with [Co(ox)3]3- (en is ethane-1,2-diamine and ox is oxalate).

The X-ray structure of racemic tris(ethane-1,2-diamine-κ2N,N')cobalt(III) tris(oxalato-κ2O1,O2)cobaltate(III) pentahydrate, [Co(C2H8N2)3][Co(C2O4)3]·5H2O or [Co(en)3][Co(ox)3]·5H2O, has been determined. Hydrogen-bonding interactions along the C3-axis of the [Co(en)3]3+ cation with the [Co(ox)3]3- anion are heterochiral, while those perpendicular to this axis are homochiral. Implications for the interpretation of chiral discriminations and induction in electron-transfer reactions in solution are discussed.

Electrochemical impedance and X-ray absorption spectroscopy analyses of degradation in dye-sensitized solar cells containing cobalt tris(bipyridine) redox shuttles.

Electrochemical impedance spectroscopy (EIS) is a commonly used steady-state technique to examine the internal resistance of electron-transfer processes in solar cell devices, and the results are directly related to the photovoltaic performance. In this study, EIS was performed to study the effects of accelerated ageing, aiming for insights into the degradation mechanisms of dye-sensitized solar cells (DSSCs) containing cobalt tris(bipyridine) complexes as redox mediators. Control experiments based on aged electrolytes differing in concentrations of the redox couple components and cation co-additives were conducted to reveal the correlation of the cell degradation with external and internal properties. The failure modes of the cells emerged as changes in the kinetics of charge- and ion-transfer processes. An insufficient concentration of the redox complexes, in particular Co(III), was found to be the main reason for the inferior performance after ageing. The related characterization of electrolytes aged outside the solar cell devices confirms the loss of active Co(III) complexes in the device electrolytes. A new EIS feature at low frequencies emerged during ageing and was analysed. The new EIS feature demonstrates the presence of an unexpected rate-limiting, charge-transfer process in aged devices, which can be attributed to the TiO2/electrolyte interface. High-resolution fluorescence detected X-ray absorption spectroscopy (HERFD-XAS) was performed to identify the reduction of a part of Co(III) to Co(II) after ageing, by investigating the Co K absorption edge. The HERFD-XAS data suggested a partial reduction of Co(III) to Co(II), accompanied by a difference in symmetry of the reduced species.

Double-network thermocells with extraordinary toughness and boosted power density for continuous heat harvesting

Double-network thermocells with extraordinary toughness and boosted power density for continuous heat harvesting

Chiral Cobalt(III) Tris(1,2-diamine) Catalysts That Incorporate Nitrogenous Base Containing Anions for the Bifunctional Activation of Nucleophiles and Electrophiles in Enantioselective Addition Reactions

Chiral Cobalt(III) Tris(1,2-diamine) Catalysts That Incorporate Nitrogenous Base Containing Anions for the Bifunctional Activation of Nucleophiles and Electrophiles in Enantioselective Addition Reactions

Understanding the role of fluorination in the mechanistic nature of the water splitting process catalyzed by cobalt tris-(2-pyridylmethyl)amine complexes

We report the mechanism of the oxygen evolution reaction catalyzed by [(CoV(TPA-αF3)(O))]3+ (TPA = tris-(2-pyridylmethyl)amine) and [(CoV(TPA-αF3)(O)OH)]2+ complexes for the formation of an oxygen–oxygen bond and the role of fluorination with the help of DFT calculations.

Solvothermal preparation of nano cobalt sulfide from tris (cyclohexylpiperazinedithiocarbamato)cobalt(III) and characterization, single crystal X-ray crystal structure of the precursor

Solvothermal formation of CoS nano particles is reported with a cobalt(III) dithiocarbamate as a single source precursor. Morphology and composition of the nano product have been characterized by PXRD and EDX analysis. Four unsymmetrically substituted tris cobalt(III) compounds, [Co(chmdtc)3] (1), [Co(chedtc)3] (2), [Co(achdtc)3] (3), and [Co(chpdtc)3] (4) (where chmdtc = cyclohexylmethylcarbodithioate, chedtc = cyclohexylethylcarbodithioate, achdtc = allylcyclohexylcarbodithioate and chpdtc = cyclohexylpiperazinecarbodithioate) were synthesized and characterized. Compounds (1)– (4) show bands at 634, 642, 635, and 643 nm respectively, due to d-d transitions. One electron quasi reversible reductions due to Co(III)/Co(II) redox process are observed in CV. In the 13C NMR spectra of the complexes, the thioureide (N13CS2) carbons resonate between 203.8 and 205.7 ppm. The observed deshielding of the –CH2 protons in 1H NMR of the compounds is attributed to the shift of electron density on the sulfur (or the metal) through the thioureide π system. TGA supported the proposed formulas of the compounds. Single crystal X-ray structure of [Co(chpdtc)3] (4) shows that the cobalt is in a distorted octahedral environment. Bond Valence Sum (BVS) calculations confirmed the formal oxidation state of cobalt as +3.

Building Block Design for Rapid Mass Transport in Quasi-Solid-State Solar Cells

Mesoscopic solar cells have rapidly emerged as a promising alternative to conventional silicon photovoltaics due to the combined benefits of low-cost, simple fabrication and competitive solar energy conversion efficiency. Recent success in low light absorption cobalt (II/III) polypyridyl complexes has led to encouraging solar energy conversion efficiencies in excess of 13%. Moreover, as one-electron redox mediators, cobalt (II/III) complexes based DSC systems also show a lower overpotential for dye regeneration and better compatibility with flexible metal substrates than iodide/tri-iodide. Such efforts open up great possibilities towards commercial applications.In contrast to the conventional organic liquid electrolytes that commonly have challenges durable encapsulation of the devices due to solvent evaporation, gel electrolytes have exhibited an impressive long-term stability, especially for outdoor applications where temperature of the DSC system can reach 80-85 oC under sunlight. Improvement on mass transport of the considerably large sized cobalt (II/III) complexes, particularly in high viscosity electrolyte, is crucial for solid-state dye-sensitized solar cells (SS-DSCs) to reach a reliable high efficiency toward practical applications.In this work, titania nanorod aggregates (TNA) with a great specific surface area and well-developed crystalline network were synthesized through a solvothermal approach and utilized as photoanode building blocks for application in cobalt (II/III) tris(2′2-bipyridine) complexes based solid-state electrolyte. An initial efficiency excess 7.1% and a long term stable efficiency of approximately 8.0% were achieved at full sun illumination by freshly assembled and aged TNA SS-DSCs, respectively. This represents dramatic enhancements of nearly 35% and 100% against the SS-DSCs prepared from two standard TiO2 nanoparticle samples – CCIC (approx. 5.9%) and Degussa P25 (approx. 4.0%), correspondingly. The TNA is characterised by a combination of mesopores within each aggregate and macro inter-aggregates voids, a high specific surface area and a great light scattering ability; such features make the aggregates superior photoanode building blocks for the application in bulky cobalt redox mediator based SS-DSCs system.

Computational insight into magnetic behaviour of cobalt tris(2-pyridylmethyl)amine complexes with dioxolenes incorporating stable radicals

A computational DFT UTPSSh/6–311++G(d,p) modelling of a series of cobalt complexes with tris(2-pyridylmethyl)amine derivatives and dioxolenes functionalized with nitronylnitroxide or 1,2,3,5-dithiadiazolyl moieties was performed. The possibility of the occurrence of magnetic bistability mechanisms was predicted. The dependence of character and strength of the exchange interactions between the paramagnetic centres on the nature of radical group and way of attachment of the latter (directly or via phenylene linker) was revealed. The comparison of the results obtained with those found for analogous compounds non-comprising radical substituents allows one to plan the directional synthesis of new paramagnetic species undergoing spin-state switching rearrangements.

Role of Metal Ion-Linked Multilayer Thickness and Substrate Porosity in Surface Loading, Diffusion, and Solar Energy Conversion.

Metal ion-linked multilayers offer an easily prepared and modular architecture for controlling energy and electron transfer events on nanoparticle, metal oxide films. However, unlike with planar electrodes, the mesoporous nature of the films inherently limits both the thickness of the multilayer and subsequent diffusion through the pores. Here, we systematically investigated the role of TiO2 nanoparticle film porosity and metal ion-linked multilayer thickness in surface loading, through-pore diffusion, and overall device performance. The TiO2 porosity was controlled by varying TiO2 sintering times. Molecular multilayer thickness was controlled through assembling ZnII-linked bridging molecules (B = p-terphenyl diphosphonic acid) between the metal oxide and the Ru(bpy)2((4,4'-PO3H2)2bpy)]Cl2 dye (RuP), thus producing TiO2-(Bn)-RuP films. Using attenuated total reflectance infrared absorption and UV-vis spectroscopy, we observed that at least two molecular layers (i.e., TiO2-B2 or TiO2-B1-RuP) could be formed on all films but subsequent loading was dependent on the porosity of the TiO2. Rough estimates indicate that in a film with 34 nm average pore diameter, the maximum multilayer film thickness is on the order of 4.6-6 nm, which decreases with decreasing pore size. These films were then incorporated as the photoanodes in dye-sensitized solar cells with cobalt(II/III)tris(4,4'-di-tert-butyl-2,2'-bipyridine) as a redox mediator. In agreement with the surface-loading studies, electrochemical impedance spectroscopy measurements indicate that mediator diffusion is significantly hindered in films with thicker multilayers and less porous TiO2. Collectively, these results show that care must be taken to balance multilayer thickness, substrate porosity, and size of the mediator in designing and maximizing the performance of new multilayer energy and electron management architectures.

Exploring Lewis-Base Effects to Improve the Efficiency of [Co(bpy)3]2+/3+-Mediated Dye-Sensitized Solar Cells

The state-of-the-art cobalt(II/III) tris(bipyridyl) redox shuttles open a chapter for pursuing highly efficient dye-sensitized solar cells (DSSCs). Previous work has demonstrated that light exposur...

Sol–gel approach for the growth of vertically aligned 3D-TiO2 nanorod arrays as an efficient photoanode for high-performance dye-sensitized solar cells

In this study, a facile, low cost, and scalable sol–gel method has been proposed for the coating of ultra-thin layer of TiO2 on FTO substrate as a seed layer for the growth of 3D-TiO2 nanorod (3D-TiO2-NR) arrays on FTO. Then, the two-step hydrothermal process including nanorod growth and the chemical etching treatment was proceeded for the fabrication of FTO/3D-TiO2-NR photoanodes. The thickness of the deposited TiO2 in FTO/TiO2-sg samples was measured with small-angle X-ray scattering technique, and it was obtained to be 21.3 nm. FE-SEM and TEM techniques were used for the morphological characterization of 3D-TiO2-NR, and it was obtained that the tightly adhered film of vertically aligned 3D-TiO2-NR with two-layer nanostructuring is formed with a cubic base and a nanorods head. Finally, DSSCs with iodine-based and cobalt(II/III) tris(2,2′-bipyridine) complex-based electrolytes with two different photoanodes including 3D-TiO2-NR and TiO2-NP were assembled and their photovoltaic characteristics were investigated. For [Co(bpy)3]2+/3+ shuttle-based DSSC, the obtained power conversion efficiency (η) was about 3.5% with Jsc of 9.36 mA cm−2 in 3D-TiO2-NR-based DSSC, while η of TiO2-NP-based DSSC was about 1.4%. The results showed that employing 3D-TiO2-NR-based photoanode in DSSCs with bulky electron shuttles remarkably improves the photovoltaic characteristics of DSSCs. Electrochemical impedance spectroscopic studies also showed the lower charge transfer resistances for DSSCs with nanorod-based photoanode building blocks.

Electrocatalytic activity of cobalt tris(4-nitrophenyl)corrole for hydrogen evolution from water

Catalytic activities for hydrogen (H2) evolution of cobalt 5,10,15-tris(phenyl)corrole (1) and 5,10,15-tris(4-nitrophenyl)corrole (2) (in homogeneous system was examined from acetic acid and water. In phosphate buffer solution (pH 7.0), the hydrogen evolution turnover frequency (TOF) for 1 and 2 were 62 and 150 h−1 at the overpotential of −1.53 V versus Ag/AgCl. In acetic acid media, hydrogen evolution TOF for 1 and 2 were 56 and 127 h−1, respectively, at an overpotential of 961 mV versus Ag/AgNO3. In the practical electrocatalytic hydrogen evolution experiment at −1.45 V (vs. Ag/AgCl) overpotential for 1 h, the TOF were 76 and 188 h−1 for 1 and 2, respectively. No observable decomposition of the catalyst could be observed after electrolysis for 72 h with a glassy carbon electrode.