Slow hole diffusion limits the efficiency of p-type dye-sensitized solar cells based on the P1 dye.

NiO electrodes are widely applied in p-type dye-sensitized solar cells (DSSCs) and photoelectrochemical cells, but due to excessive charge recombination, the efficiencies of these devices are still too low for commercial applications. To understand which factors induce charge recombination, we studied electrodes with a varying number of NiO layers in benchmark P1 p-DSSCs. We obtained the most efficient DSSCs with four layers of NiO (0.

Substrate scope driven optimization of an encapsulated hydroformylation catalyst.

Caged complexes can provide impressive selective catalysts. Due to the complex shapes of such caged catalysts, however, the level of selectivity control of a single substrate cannot be extrapolated to other substrates. Herein, the substrate scope using 41 terminal alkene substrates is investigated in the hydroformylation reaction with an encapsulated rhodium catalyst [Rh(H)(CO)(P(Py(ZnTPP)))] ().

PdML (for = 6, 8, 12) nanospheres by post-assembly modification of PdL spheres.

In this contribution, we describe a post-assembly modification approach to selectively coordinate transition metals in PdL cuboctahedra. The herein reported approach involves the preparation of PdL nanospheres with protonated nitrogen donor ligands that are covalently linked at the interior. The so obtained Pd(LH) nanospheres are shown to be suitable for coordinative post-modification after deprotection by deprotonation.

biodistribution of kinetically stable PtL nanospheres that show anti-cancer activity.

There is an increasing interest in the application of metal-organic cages (MOCs) in a biomedicinal context, as they can offer non-classical distribution in organisms compared to molecular substrates, while revealing novel cytotoxicity mechanisms. Unfortunately, many MOCs are not sufficiently stable under conditions, making it difficult to study their structure-activity relationships in living cells. As such, it is currently unclear whether MOC cytotoxicity stems from supramolecular features or their decomposition products.

Entropy directs the self-assembly of supramolecular palladium coordination macrocycles and cages.

The self-assembly of palladium-based cages is frequently rationalized the cumulative enthalpy (Δ) of bonds between coordination nodes (M, , Pd) and ligand (L) components. This focus on enthalpic rationale limits the complete understanding of the Gibbs free energy (Δ) for self-assembly, as entropic (Δ) contributions are overlooked. Here, we present a study of the M L intermediate species (M = dinitrato(,,','-tetramethylethylenediamine)palladium(ii), L = 4,4'-bipyridine), formed during the synthesis of triangle-shaped (M L) and square-shaped (M L) coordination macrocycles.

Kinetic studies on Lewis acidic metal polyesterification catalysts - hydrolytic degradation is a key factor for catalytic performance.

Kinetic analysis of polyesterification reactions using Lewis-acidic metal catalysts have been performed. While Sn-based catalysts are superior to Ti-based catalysts under neat polycondensation conditions (high [HO]), the result is inverted under azeotropic conditions (low [HO]). These findings show that the catalytic activity is crucially determined by the robustness of the catalyst against hydrolytic degradation.

Comparison of homogeneous and heterogeneous catalysts in dye-sensitised photoelectrochemical cells for alcohol oxidation coupled to dihydrogen formation.

This study examines two strategies-homo- and heterogeneous approaches for the light-driven oxidation of benzyl alcohol in dye-sensitised photoelectrochemical cells (DSPECs). The DSPEC consists of a mesoporous anatase TiO film on FTO (fluorine-doped tin oxide), sensitised with the thienopyrroledione-based dye as the photoanode and an FTO-Pt cathode combined with a redox-mediating catalyst. The homogeneous catalyst approach entails the addition of the soluble 2,2,6,6-tetramethylpiperidine-1-oxyl () to the DSPEC anolyte, while the heterogeneous strategy employs immobilisation of a analogue with a silatrane anchor () onto the photoanode.

Selective formation of PtL nanospheres by ligand design.

Supramolecular self-assemblies are used across various fields for different applications including their use as containers for catalysts, drugs and fluorophores. ML spheres are among the most studied, as they offer plenty of space for functionalization, yielding systems with unique properties in comparison to their single components. Detailed studies on the formation of ML structures using palladium cornerstones (that have generally dynamic coordination chemistry) aided in the development of synthetic protocols.

Supramolecular strategies in artificial photosynthesis.

Artificial photosynthesis is a major scientific endeavor aimed at converting solar power into a chemical fuel as a viable approach to sustainable energy production and storage. Photosynthesis requires three fundamental actions performed in order; light harvesting, charge-separation and redox catalysis. These actions span different timescales and require the integration of functional architectures developed in different fields of study.

Mechanistic elucidation of monoalkyltin(iv)-catalyzed esterification.

Monoalkyltin(iv) complexes are well-known catalysts for esterification reactions and polyester formation, yet the mode of operation of these Lewis acidic complexes is still unknown. Here, we report on mechanistic studies of -butylstannoic acid in stoichiometric and catalytic reactions, analyzed by NMR, IR and MS techniques. While the chemistry of -butyltin(iv) carboxylates is dominated by formation of multinuclear tin assemblies, we found that under catalytically relevant conditions only monomeric -BuSn(OAc) and dimeric (-BuSnOAcOEt) are present.

Topological prediction of palladium coordination cages.

The preparation of functionalized, heteroleptic Pd L coordination cages is desirable for catalytic and optoelectronic applications. Current rational design of these cages uses the angle between metal-binding (∠) sites of the di(pyridyl)arene linker to predict the topology of homoleptic cages obtained non-covalent chemistry. However, this model neglects the contributions of steric bulk between the pyridyl residues-a prerequisite for endohedrally functionalized cages, and fails to rationalize heteroleptic cages.

A Fluorescence-Based Screening Protocol for the Identification of Water Oxidation Catalysts.

Efficient catalysts are crucial for the sustainable generation of fuel by splitting water. A versatile screening protocol would simplify the identification of novel and better catalysts by using high throughput experimentation. Herein, such a screening approach for the identification of molecular catalysts for chemical oxidation of water is reported, which is based on oxygen-sensitive fluorescence quenching using an OxoDish.