Polyoxometalates (POMs) are a subset of metal oxides that represent a diverse range of molecular clusters with an almost unmatched range of physical properties and the ability to form dynamic structures that can range in size from the nano- to the micrometer scale Herein we present the very latest developments from synthesis to structure and function of POMs We discuss the possibilities of creating highly sophisticated functional hierarchical systems with multiple, interdependent, functionalities along with a critical analysis that allows the non-specialist to learn the salient features We propose and present a "periodic table of polyoxometalate building blocks" We also highlight some of the current issues and challenges that need to be addressed to work towards the design of functional systems based upon POM building blocks and look ahead to possible emerging application areas

Polyoxometalates: Building Blocks for Functional Nanoscale Systems

We introduce density functional theory and review recent progress in its application to transition metal chemistry. Topics covered include local, meta, hybrid, hybrid meta, and range-separated functionals, band theory, software, validation tests, and applications to spin states, magnetic exchange coupling, spectra, structure, reactivity, and catalysis, including molecules, clusters, nanoparticles, surfaces, and solids.

Density functional theory for transition metals and transition metal chemistry

Hydrogels for biomedical applications.

ion and completion of the cyclometalation reaction are feasible and produce the cyclometalated complex 205. Notably, addition of a strong acid reverts the cyclometalation and regenerates the agostic species 204. Small changes in the rhodium precursor significantly modify the product outcome and lead at fast rates to the cyclometalated complex 203, that is, the final oxidative addition product S. Similarly, alkene C-H bond activation has been observed to occur readily in a PCP ligand setting.348 Milstein and co-workers developed a procedure for preparing the cyclometalated PCP, PCN, or PCO pincer complexes 209 by rhodium-mediated cleavage of a strong Caryl-Calkyl bond (Scheme 87).32,349,350 Kinetically, Calkyl-H bond activation is competitive and complex 208 is formed as a second product at essentially similar rates. However, C-C bond cleavage appears to be the thermodynamically more favored process. Obviously, the higher energy required for Caryl-Calkyl bond activation (bond dissociation energy 427 kJ mol-1) compared to C-H bond breaking (368 kJ mol-1) is compensated by the stronger Rh-Caryl bond and the formation of two fiverather than six-membered metallacycles. Because rhodium-mediated Caryl-Calkyl and Calkyl-H bond activations in 206 are thermodynamically and kinetically very similar processes,351 subtle changes in the ligand parameters strongly affect the reaction outcome. For example, PPh2 donors induce C-H bond cleavage to afford 208d exclusively at ambient temperatures. C-C activation and formation of 209d is only induced upon heating under H2 atmosphere,352 presumably because these conditions allow the product selectivity to be controlled thermodynamically. In contrast, bulky PtBu2 donors as in 206a promote C-C bond activation already at room temperature, and the aryl complex 209a is the only product observed. Similarly, replacing one phosphine donor by a harder NEt2 group or the use of less basic phosphinite donors results in selective C-C bond cleavage at room temperature. These preferences suggest steric factors to play a more dominant role than electronic differences in determining the C-C vs C-H selectivity. Steric congestion induced by the donor substituents has been proposed to arrange the orbitals of the metal center to be directed toward the C-C bond rather than toward the C-H bond.353 Kinetic investigations have identified the coordination compound 207 as a common intermediate of Calkyl-H and the Caryl-Calkyl bond activation. On the basis of the similar rates for both cleavage processes and because of the absence of any detectable intermediate, formation of 207 and not C-H or C-C bond activation appears to be rate-limiting. While displacement of a weakly bound olefin ligand in the metal precursor may be fast, formation of the 8-membered metallacycle in 207 may be less favored, especially due to the potential for forming diand polymeric coordination compounds. It is worth noting that, upon substituting the PCP pincer ligand to a PCN donor array, the coordination complex 207c becomes stable at low temperature and has been spectroscopically characterized.354 As a consequence, the rate-determining step is shifted to a later stage on the reaction coordinate. Notably, slight modifications in the metal precursor, that is, utilization of [Rh(C2H4)(CO)(solv)2]BF4 instead of [RhCl(C2H4)2]2, alters the stability of the intermediates and produces complex 210 (Scheme 88).355 This complex may be represented by an agostic interaction of the C-C bond with the rhodium center, or alternatively by an arenium structure including an sp3-hybridized ipso carbon. Because of only weak Cipso-Rh interactions in solution (e.g., the absence of any 103Rh coupling), the agostic description is favored. The different product outcome has been presumed to originate from the reduced electron density at the cationic rhodium(I) center due to the strongly withdrawing CO ligand and the relatively weak Rh-N bond. This configuration Scheme 87 Scheme 86 Cyclometalation Using d-Block Transition Metals Chemical Reviews, 2010, Vol. 110, No. 2 603

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Cyclometalation Using d-Block Transition Metals: Fundamental Aspects and Recent Trends

Recent advances on polysaccharides, lipids and protein based edible films and coatings: A review.

Effects of carboxymethyl cellulose and chitosan bilayer edible coating on postharvest quality of citrus fruit.

Many important biological and chemical processes, including photocatalytic water oxidation to molecular oxygen (of interest as a route to artificial photosynthesis) and the activation of dioxygen on metal surfaces, are thought to involve transition metal terminal oxo complexes. Poverenov et al. now report the synthesis of a platinum based oxidizing reagent with potentially useful characteristics. It's a d6 Pt(IV) terminal oxo complex that is not stabilized by an electron accepting ligand framework, and so exhibits reactivity as both an inter- and intra-molecular oxygen donor and as an electrophile. It also undergoes water activation to produce a terminal dihydroxo complex, which may be of relevance to the mechanism of water oxidation and other catalytic reactions. Terminal oxo complexes of transition metals are important in biological and chemical processes, for example, the catalytic oxidation of organic molecules and the activation of dioxygen on metal surfaces are thought to involve oxo complexes. This paper explored the reactivity of a d6 Pt(IV) complex, a dn (n > 5) terminal oxo complex that is not stabilized by an electron withdrawing ligand framework. The complex exhibits reactivity as an inter- and intra-molecular oxygen donor and as an electrophile. Terminal oxo complexes of transition metals have critical roles in various biological and chemical processes1,2. For example, the catalytic oxidation of organic molecules3,4, some oxidative enzymatic transformations5,6,7, and the activation of dioxygen on metal surfaces8 are all thought to involve oxo complexes. Moreover, they are believed to be key intermediates in the photocatalytic oxidation of water to give molecular oxygen, a topic of intensive global research aimed at artificial photosynthesis and water splitting9,10,11,12,13. The terminal oxo ligand is a strong π-electron donor, so it readily forms stable complexes with high-valent early transition metals. As the d orbitals are filled up with valence electrons, the terminal oxo ligand becomes destabilized2. Here we present evidence for a dn (n > 5) terminal oxo complex that is not stabilized by an electron withdrawing ligand framework. This d6 Pt(iv) complex exhibits reactivity as an inter- and intramolecular oxygen donor and as an electrophile. In addition, it undergoes a water activation process leading to a terminal dihydroxo complex, which may be relevant to the mechanism of catalytic reactions such as water oxidation.

Evidence for a terminal Pt(iv)-oxo complex exhibiting diverse reactivity

Development of polysaccharides-based edible coatings for citrus fruits: a layer-by-layer approach.

Edible coatings attract interest today as efficient and safe techniques for controlling the deterioration and extending the shelf-life of food products. In the present study, a layer-by-layer (LbL) electrostatic deposition of oppositely charged natural polysaccharides, a polyanion alginate and a polycation chitosan, was implemented for coating a model food: fresh-cut melon. The performance of the alginate–chitosan coating was compared with single-layer coatings and with non-coated control. The LbL coating was found to possess the beneficial properties of both ingredients, combining good adhesion to melon matrix of the inner alginate layer with antimicrobial activity of the outer chitosan layer, thereby reducing the bacteria, yeast, and fungi counts by 1–2 log CFU. The bilayer coating slowed down tissue texture degradation, so that after 14 days of storage only LbL samples maintained an appreciable firmness. An unexpected benefit of the LbL coating was that its enhanced gas-exchange properties exceeded those of both monolayer coatings and even of the non-coated control. As a result, the LbL coating prevented an increase in headspace CO2 and ethanol concentrations, which are the signs of hypoxic stress and off-flavor development observed in other samples, especially in alginate-coated melons. The phenomenon was presumably related to swelling behavior of the chitosan layer in the humid atmosphere of the fresh-cut melon package, giving the melon pieces an attractive succulent appearance. At the same time, the LbL coating resulted in somewhat increased produce weight loss due to the reduced surface water vapor resistance. The method is cheap, simple, and can improve the quality and safety of food products.

Layer-by-Layer Electrostatic Deposition of Edible Coating on Fresh Cut Melon Model: Anticipated and Unexpected Effects of Alginate–Chitosan Combination

Hydrogels are important materials that are of high scientific interest and with numerous applications. Natural polymer-based hydrogels are preferred to synthetic ones due to their safety, biocompatibility, and ecofriendly properties. They have been studied extensively and implemented in various fields, such as medicine, cosmetics, personal-care products, water purification, and more. This review focuses on the applications of nature-sourced polymer-based hydrogels in food and agriculture. Different types of biopolymers and crosslinking agents, and various methods for hydrogel formation are described. The physicomechanical properties and applied activities of the resulting materials are also comprehensively discussed. Biodegradable synthetic polymers are outside the scope of this review. © 2020 Society of Chemical Industry.

Elena Poverenov

Papers

Effects of carboxymethyl cellulose and chitosan bilayer edible coating on postharvest quality of citrus fruit.

Evidence for a terminal Pt(iv)-oxo complex exhibiting diverse reactivity

Development of polysaccharides-based edible coatings for citrus fruits: a layer-by-layer approach.

Layer-by-Layer Electrostatic Deposition of Edible Coating on Fresh Cut Melon Model: Anticipated and Unexpected Effects of Alginate–Chitosan Combination

Natural biopolymer-based hydrogels for use in food and agriculture.