Thiomolybdate Clusters: From Homogeneous Catalysis to Heterogenization and Active Sites.

Thiomolybdates are molecular molybdenum-sulfide clusters formed from Mo centers and sulfur-based ligands. For decades, they have attracted the interest of synthetic chemists due to their unique structures and their relevance in biological systems, e.g., as reactive sites in enzymes. More recently, thiomolybdates are explored from the catalytic point of view and applied as homogeneous and molecular mimics of heterogeneous molybdenum sulfide catalysts. This review summarizes prominent examples of thiomolybdate-based electro- and photocatalysis and provides a comprehensive analysis of their reactivities under homogeneous and heterogenized conditions. Active sites of thiomolybdates relevant for the hydrogen evolution reaction are examined, aiming to shed light on the link between cluster structure and performance. The shift from solution-phase to surface-supported thiomolybdates is discussed with a focus on applications in electrocatalysis and photocatalysis. The outlook highlights current trends and emerging areas of thiomolybdate research, ending with a summary of challenges and key takeaway messages based on the state-of-the-art research.

Initial Quenching Efficiency Determines Light-Driven H2 Evolution of [Mo3 S13 ]2- in Lipid Bilayers.

Nature uses reactive components embedded in biological membranes to perform light-driven photosynthesis. Here, a model artificial photosynthetic system for light-driven hydrogen (H2 ) evolution is reported. The system is based on liposomes where amphiphilic ruthenium trisbipyridine based photosensitizer (RuC9 ) and the H2 evolution reaction (HER) catalyst [Mo3 S13 ]2- are embedded in biomimetic phospholipid membranes. When DMPC was used as the main lipid of these light-active liposomes, increased catalytic activity (TONCAT ~200) was observed compared to purely aqueous conditions. Although all tested lipid matrixes, including DMPC, DOPG, DPPC and DOPG liposomes provided similar liposomal structures according to TEM analysis, only DMPC yielded high H2 amounts. In situ scanning electrochemical microscopy (SECM) measurements using Pd microsensors revealed an induction period of around 26 minutes prior to H2 evolution, indicating an activation mechanism which might be induced by the fluid-gel phase transition of DMPC at room temperature. Stern-Volmer-type quenching studies revealed that electron transfer dynamics from the excited state photosensitizer are most efficient in the DMPC lipid environment giving insight for design of artificial photosynthetic systems using lipid bilayer membranes.

Diiodo-BODIPY Sensitizing of the [Mo3S13]2- Cluster for Noble-Metal-Free Visible-Light-Driven Hydrogen Evolution within a Polyampholytic Matrix.

We report on a photocatalytic setup that utilizes the organic photosensitizer (PS) diiodo-BODIPY and the non-precious-metal-based hydrogen evolution reaction (HER) catalyst (NH4)2[Mo3S13] together with a polyampholytic unimolecular matrix poly(dehydroalanine)-graft-poly(ethylene glycol) (PDha-g-PEG) in aqueous media. The system shows exceptionally high performance with turnover numbers (TON > 7300) and turnover frequencies (TOF > 450 h-1) that are typical for noble-metal-containing systems. Excited-state absorption spectra reveal the formation of a long-lived triplet state of the PS in both aqueous and organic media. The system is a blueprint for developing noble-metal-free HER in water. Component optimization, e.g., by modification of the meso substituent of the PS and the composition of the HER catalyst, is further possible.

Not that innocent - ammonium ions boost homogeneous light-driven hydrogen evolution.

We report that the homogeneous light-driven hydrogen evolution reaction (HER) can be significantly enhanced by the presence of seemingly innocent ammonium (NH4+) cations. Experimental studies with different catalysts, photosensitizers and electron donors show this to be a general effect. Preliminary photophysical and mechanistic studies provide initial suggestions regarding the role of ammonium in the HER enhancement.

A photosensitizer-polyoxometalate dyad that enables the decoupling of light and dark reactions for delayed on-demand solar hydrogen production.

Decoupling the production of solar hydrogen from the diurnal cycle is a key challenge in solar energy conversion, the success of which could lead to sustainable energy schemes capable of delivering H2 independent of the time of day. Here, we report a fully integrated photochemical molecular dyad composed of a ruthenium-complex photosensitizer covalently linked to a Dawson polyoxometalate that acts as an electron-storage site and hydrogen-evolving catalyst. Visible-light irradiation of the system in solution leads to charge separation and electron storage on the polyoxometalate, effectively resulting in a liquid fuel. In contrast to related, earlier dyads, this system enables the harvesting, storage and delayed release of solar energy. On-demand hydrogen release is possible by adding a proton donor to the dyad solution. The system is a minimal molecular model for artificial photosynthesis and enables the spatial and temporal separation of light absorption, fuel storage and hydrogen release.

Increased in vitro Anti-HIV Activity of Caffeinium-Functionalized Polyoxometalates.

Polyoxometalates (POMs), molecular metal oxide anions, are inorganic clusters with promising antiviral activity. Herein we report increased anti-HIV-1 activity of a POM when electrostatically combined with organic counter-cations. To this end, Keggin-type cerium tungstate POMs have been combined with organic methyl-caffeinium (Caf) cations, and their cytotoxicity, antiviral activity and mode of action have been studied. The novel compound, Caf4 K[ß2 -CeSiW11 O39 ]×H2 O, exhibits sub-nanomolar antiviral activity and inhibits HIV-1 infectivity by acting on an early step of the viral infection cycle. This work demonstrates that combination of POM anions and organic bioactive cations can be a powerful new strategy to increase antiviral activity of these inorganic compounds.

Polyampholytic Graft Copolymers as Matrix for TiO2 /Eosin Y/[Mo3 S13 ]2- Hybrid Materials and Light-Driven Catalysis.

An effective strategy to enhance the performance of inorganic semiconductors is moving towards organic-inorganic hybrid materials. Here, we report the design of core-shell hybrid materials based on a TiO2 core functionalized with a polyampholytic (poly(dehydroalanine)-graft-(n-propyl phosphonic acid acrylamide) shell (PDha-g-PAA@TiO2 ). The PDha-g-PAA shell facilitates the efficient immobilization of the photosensitizer Eosin Y (EY) and enables electronic interactions between EY and the TiO2 core. This resulted in high visible-light-driven H2 generation. The enhanced light-driven catalytic activity is attributed to the unique core-shell design with the graft copolymer acting as bridge and facilitating electron and proton transfer, thereby also preventing the degradation of EY. Further catalytic enhancement of PDha-g-PAA@TiO2 was possible by introducing [Mo3 S13 ]2- cluster anions as hydrogen-evolution cocatalyst. This novel design approach is an example for a multi-component system in which reactivity can in future be independently tuned by selection of the desired molecular or polymeric species.

Experimental and Theoretical Investigation of the Light-Driven Hydrogen Evolution by Polyoxometalate-Photosensitizer Dyads.

The visible-light-driven hydrogen evolution reaction (HER) by covalent photosensitizer-catalyst dyads is one of the most elegant concepts in supramolecular homogeneous solar energy conversion. The intricacies of catalyst reactivity and photosensitizer-catalyst interactions require a detailed fundamental understanding of the system to rationalize the observed reactivities. Here, we report three dyads based on the covalent imine-bond linkage of an iridium photosensitizer and an organo-functionalized Anderson polyoxometalate anion [MMo6 O18 {(OCH2 )3 CNH2 }2 ]3- (M=Mn3+ , Fe3+ , Co3+ ). Modification of the central metal ion M is used to modulate the HER activity. Detailed theoretical and experimental studies examine the role of the central metal ion M and provide critical understanding of the redox activity and light-driven HER activity of the novel dyads. Thus, the study enables a knowledge-based optimization of HER dyads by chemical modification of the reactive metal oxide components.

Homogeneous and Heterogeneous Anion Sensing by a Molecular Cobalt-Vanadium Oxide.

Spectroscopic anion sensing is a vital non-invasive tool in chemistry and biology. Here, a molecular cobalt-vanadium-oxide cluster was shown to be capable of selectively binding and detecting various mono-anions in solution and immobilized on a solid support. The cluster anion [Co(X)V4 O12 ]3- (X=mono-anion, for example, halide, pseudohalide, carboxylate, etc.) was formed spontaneously upon anion addition by self-assembly in solution. The cluster showed distinct spectral changes upon anion binding that could be followed spectroscopically and visually owing to a significant change of the solution color. DFT computations showed that the anion binding observed experimentally was correlated to the relative cluster stabilities. Competitive-binding studies showed that selective anion binding was possible from a mixture of anions. Immobilization of the anion sensor on silica strips provided access to single-use dip-stick sensors for the facile detection of anions in solution. The system presented enables the development of homogeneous or heterogeneous molecular anion sensors with possible applications in chemistry, bio-medical scenarios, and under harsh environmental conditions.

The anion-binding polyanion: a molecular cobalt vanadium oxide with anion-sensitive visual response.

An anionic molecular cobalt vanadium oxide cluster, (n-Bu4N)3[Co(AcO)V4O12] and its use as anion binding site is reported. Cluster formation is controlled by an anion-dependent dynamic solution equilibrium. Reversible anion binding in solution leads to significant spectral changes, allowing the ratiometric optical detection of the anion concentration in situ, even under harsh thermal conditions (T = 90 °C). Comparative studies showed that the spectral response is dependent on the type of anion so that carboxylates, weakly coordinating anions and halides can be distinguished.