Leone Spiccia

This paper reports the synthesis and characterisation of a family of heterocyclic triethoxysilyl iodides of general formula, (EtO)₃SiR²-N⁺R¹, where R¹ = –C₅H₁₁, –CH₂C₆H₅ or –C₁₆H₃₃; N⁺ = pyrrolidinium or piperidinium; and R² = –(CH₂)₃– and –(CH₂)₁₁– and their applications as organic iodide sources for use in dye sensitised solar cells. The effect of three variations in the structure of these derivatives (viz., R¹, R² and N⁺ ) on DSSC performance has been investigated using a range of techniques, including I–V profiling at different light intensities and transient photovoltage and photocurrent measurements. The results of these analyses have been used to develop an understanding of how different organic cations interact with the DSSC on a molecular level and influence the overall performance of the device. Of the three parameters, the length of the spacer – R² – was found to have the greatest influence of device performance. Use of the organic iodides with the longer spacer – where R² = –(CH₂)₁₁– were superior in performance to those with a shorter spacer – where R² = (CH₂)₃– with devices constructed using the silyl iodide with longer spacer showing larger open circuit voltages and longer recombination times in comparison to those prepared using the shorter one.

Layered double hydroxides are materials that show promise as adsorbing media for ink-jet printing. In this work, layered double hydroxides with nitrate as interlayer anions and with variable Mg:Al molar ratios ranging from 2.2 to 8.1 have been synthesized at constant pH by the coprecipitation method and characterized by powder X-ray diffraction, N2 adsorption–desorption, scanning electron microscopy, and helium pycnometry techniques. The ability of these materials to adsorb ink-jet inks (BCI-Cyan, BCI-Yellow, and BCI-Magenta) and anionic dyes (CI Acid Blue 9 (AB9), CI Acid Yellow 23 (AY23), and CI Acid Red 37 (AR37)) were investigated. BCI-Yellow was found to have high affinity for material with an Mg:Al molar ratio between 2.2 and 4.0, whereas BCI-Cyan and BCI-Magenta showed a high affinity when the Mg:Al molar ratio was between 4.8 and 5.5. The adsorption isotherms for AB9, AY23, and AR37 on the material with Mg:Al molar ratios 2.2–5.5 exhibited H-type curves, indicating a very strong interaction between the adsorbate and adsorbent. Although there was no clear systematic correlation between the MgsAl molar ratio and the Cm (dye capacity) and Ka (dye affinity), the optimum Mg:Al molar ratio was 4.0, and this material has the potential to be used in Ink-Receptive Layer formulation.

The new ligand, [Fc(cyclen)₂] (5) (Fc=ferrocene, cyclen=1,4,7,10-tetraazacyclododecane), and corresponding Zn^II complex receptor, [Fc{Zn(cyclen)(CH₃OH)}₂](ClO₄)₄ (1), consisting of a ferrocene moiety bearing one Zn^II-cyclen complex on each cyclopentadienyl ring, have been designed and prepared through a multi-step synthesis. Significant shifts in the ¹H NMR signals of the ferrocenyl group, cf. ferrocene and a previously reported [Fc{Zn(cyclen)}]²⁺ derivative, indicated that the two Zn^II-cyclen units in 1 significantly affect the electronic properties of the cyclopentadienyl rings. The X-ray crystal structure shows that the two positively charged Zn^II-cyclen complexes are arranged in a trans like configuration, with respect to the ferrocene bridging unit, presumably to minimise electrostatic repulsion. Both 5 and 1 can be oxidized in 1:4 CH₂Cl₂/CH₃CN and Tris-HCl aqueous buffer solution under conditions of cyclic voltammetry to give a well defined ferrocene-centred (Fc^0/+) process. Importantly, 1 is a highly selective electrochemical sensor of thymidilyl(3′-5′)thymidine (TpT) relative to other nucleobases and nucleotides in Tris-HCl buffer solution (pH 7.4). The electrochemical selectivity, detected as a shift in reversible potential of the Fc^0/+ component, is postulated to result from a change in the configuration of bis(Zn^II-cyclen) units from a trans to a cis state. This is caused by the strong 1:1 binding of the two deprotonated thymine groups in TpT to different Zn^II centres of receptor 1. UV-visible spectrophotometric titrations confirmed the 1:1 stoichiometry for the 1:TpT adduct and allowed the determination of the apparent formation constant of 0.89±0.10×10⁶ M⁻¹ at pH 7.4.

Photoelectrochemical cells that efficiently split water into oxygen and hydrogen, “the fuel of the future”, need to combine robust water oxidation catalysts at the anode (2H₂O → O₂ + 4H⁺ + 4e⁻) with hydrogen reduction catalysts at the cathode (2H⁺ + 2e⁻→ H₂). Both sets of catalysts will, ideally, operate at low overpotentials and employ light-driven or light-assisted processes. In this Perspective article, we focus on significant efforts to develop solid state materials and molecular coordination complexes as catalyst for water oxidation. We briefly review the field with emphasis on the various molecular catalysts that have been developed and then examine the activity of molecular catalysts in water oxidation following their attachment to conducting electrodes. For such molecular species to be useful in a solar water-splitting device it is preferable that they are securely and durably affixed to an electrode surface. We also consider recent developments aimed at combining the action of molecular catalysts with light absorption so that light driven water oxidation may be achieved.

Chemical surface treatment of porphyrin-sensitised titania films using bis-(4-methoxyphenyl)phosphinic acid after dye adsorption, results in large improvements in DSSC efficiencies which originate primarily from higher short circuit currents. The result was attributed to a positive shift in the TiO₂ quasi-Fermi level with simultaneous retardation of charge recombination. High device performances have been achieved even using simplified electrolyte matrices devoid of the common additives, LiI and t-butylpyridine.

High valence states in manganese clusters are a key feature of the function of one of the most important catalysts found in nature, the water-oxidizing complex of photosystem II. We describe a detailed electrochemical investigation of two bio-inspired manganese–oxo complexes, [Mn₄O₄L₆] (L = diphenylphosphinate (1) and bis(p-methoxyphenyl)phosphinate (2)), in solution, attached to an electrode surface and suspended within a Nafion film. These complexes contain a cubic [Mn₄O₄]⁶⁺ core stabilized by phosphinate ligands. They have previously been shown to be active and durable photocatalysts for the oxidation of water to dioxygen. A comparison of catalytic photocurrent generated by films deposited by two methods of electrode immobilization reveals that doping of the catalyst in Nafion results in higher photocurrent than was observed for a solid layer of cubane on an electrode surface. In dichloromethane solution, and under conditions of cyclic voltammetry, the one-electron oxidation processes 1/1⁺ and 2/2⁺ were found to be reversible and quasi-reversible, respectively. Some decomposition of 1⁺ and 2⁺ was detected on the longer timescale of bulk electrolysis. Both compounds also undergo a two-electron, chemically irreversible reduction in dichloromethane, with a mechanism that is dependent on scan rate and influenced by the presence of a proton donor. When immersed in aqueous electrolyte, the reduction process exhibits a limited level of chemical reversibility. These data provide insights into the catalytic operation of these molecules during photo-assisted electrolysis of water and highlight the importance of the strongly electron-donating ligand environment about the manganese ions in the ability of the cubanes to photocatalyze water oxidation at low overpotentials.

The rate and activation parameters for oxygen exchange of the μ₃-oxo bridges in a manganese tetranuclear cluster with H₂ ¹⁸O have been measured by ESI-MS; the observed ΔS^‡ of −146 ± 22 J K^−1.mol⁻¹ is consistent with the expected associative mechanism of substitution.