Electronic Consequences of Ligand Substitution at Heterometal Centers in Polyoxovanadium Clusters: Controlling the Redox Properties through Heterometal Coordination Number

The rational control of the electrochemical properties of polyoxovanadate‐alkoxide clusters is dependent on understanding the influence of various synthetic modifications on the overall redox processes of these systems. In this work, the electronic consequences of ligand substitution at the heteroion in a heterometal‐functionalized cluster was examined. The redox properties of [V$_{5}$O$_{6}$(OCH$_{3}$)$_{12}$FeCl] (1‐[V$_{5}$FeCl] ) and [V$_{5}$O$_{6}$(OCH$_{3}$)$_{12}$Fe]X (2‐[V5Fe]X ; X=ClO$_{4}$, OTf) were compared in order to assess the effects of changing the coordination environment around the iron center on the electrochemical properties of the cluster. Coordination of a chloride anion to iron leads to an anodic shift in redox events. Theoretical modelling of the electronic structure of these heterometal‐functionalized clusters reveals that differences in the redox profiles of 1‐[V$_{5}$FeCl] and 2‐[V$_{5}$Fe]X arise from changes in the number of ligands surrounding the iron center (e.g., 6‐coordinate vs. 5‐coordinate). Specifically, binding of the chloride to the sixth coordination site appears to change the orbital interaction between the iron and the delocalized electronic structure of the mixed‐valent polyoxovanadate core. Tuning the heterometal coordination environment can therefore be used to modulate the redox properties of the whole cluster

Multifunctional Polyoxometalate Platforms for Supramolecular Light-Driven Hydrogen Evolution

Multifunctional supramolecular systems are a central research topic in light-driven solar energy conversion. Here, we report a polyoxometalate (POM)-based supramolecular dyad, where two platinum-complex hydrogen evolution catalysts are covalently anchored to an Anderson polyoxomolybdate anion. Supramolecular electrostatic coupling of the system to an iridium photosensitizer enables visible light-driven hydrogen evolution. Combined theory and experiment demonstrate the multifunctionality of the POM, which acts as photosensitizer/catalyst-binding-site[1] and facilitates light-induced charge-transfer and catalytic turnover. Chemical modification of the Pt-catalyst site leads to increased hydrogen evolution reactivity. Mechanistic studies shed light on the role of the individual components and provide a molecular understanding of the interactions which govern stability and reactivity. The system could serve as a blueprint for multifunctional polyoxometalates in energy conversion and storage

Genotype-phenotype correlation in a family with Arg135Leu rhodopsin retinitis pigmentosa

Aim: To describe the clinical characteristics and disease course of a large family with retinitis pigmentosa (RP) from an Arg135Leu change in rhodopsin

Fiscal redistribution around elections when democracy is not "the only game in town"

This paper seeks to examine the implications of policy intervention around elections on income inequality and fiscal redistribution. We first develop a simplified theoretical framework that allows us to examine election-cycle fiscal redistribution programs in the presence of a revolutionary threat from some groups of agents, i.e., when democracy is not “the only game in town”. According to our theoretical analysis, when democracy is not “the only game in town”, incumbents implement redistributive policies not only as a means of improving their reelection prospects, but also in order to signal that “democracy works”, thereby preventing a reversion to an autocratic status quo ante at a time of the current regime’s extreme vulnerability. Subsequently, focusing on 65 developed and developing countries over the 1975–2010 period, we report robust empirical evidence of pre-electoral budgetary manipulation in new democracies. Consistent with our theory, this finding is driven by political instability that induces incumbents to redistribute income—through tax and spending policies—in a relatively broader coalition of voters with the aim of consolidating the vulnerable newly established democratic regime

The Role of Gender Information in Pronoun Resolution: Evidence from Chinese

Although previous studies have consistently demonstrated that gender information is used to resolve pronouns, the mechanisms underlying the use of gender information continue to be controversial. The present study used event-related potentials (ERPs) to investigate whether working memory modulates the effect of gender information on pronoun resolution. The critical pronoun agreed or disagreed with its antecedent in gender. Moreover, the distance between a pronoun and its antecedent was varied to assess the influence of working memory. Compared with the congruent pronouns, the incongruent pronouns elicited an N400 effect in the short distance condition and a P600 effect in the long distance condition. The results suggest that the effect of gender information on pronoun comprehension is modulated by working memory