Photo-driven water oxidation performed by supramolecular photocatalysts made of Ru(II) photosensitizers and catalysts.

Two new supramolecular photocatalysts made of covalently linked Ru(II) polypyridine chromophore subunits ([Ru(bpy)3]2+-type species; bpy = 2,2'-bipyridine) and [RuL(pic)2] (L = 2,2'-bipyridine-6,6'-dicarboxylic acid; pic = 4-picoline) water oxidation catalyst subunits have been prepared. The new species, 1 and 2, contain chromophore and catalyst subunits in the molecular ratios 1:1 and 1:2, respectively. The model chromophore species [Ru(bpy)2(L1)]2+ (RuP1; L1=4-[2-(4-pyridyl)-2-hydroxyethyl]-4-methyl-2,2'-bipyridine) and [Ru(bpy)2(L2)]2+ (RuP2; L2 = 4,4'-bis[2-(4-pyridyl)-2-hydroxyethyl]-2,2'-bipyridine) have also been prepared.

Photophysical Properties of Homo- and Hetero-Aggregate Assemblies Made of N-Annulated Perylene Derivatives.

We report the absorption spectra and photophysical properties of homo and hetero-aggregate assemblies of a strongly emissive N-annulated perylene dye (P) and of a dyad made of P and a methyl viologen derivative (P-MV), in ethanol-water solutions. In homo-aggregate assemblies of P, the π-π* fluorescence of the isolated chromophore is replaced by excimer emission at lower energy, with a lifetime of 900 ps, due to excimer formation from the initially prepared excitons. In homo-aggregate assemblies of P-MV, photoinduced charge separation, with formation of P -MV species, occurs in 3 ps with a charge recombination of 20 ps.

Design and Development of Fluorinated and Biocide-Free Sol-Gel Based Hybrid Functional Coatings for Anti-Biofouling/Foul-Release Activity.

Biofouling has destructive effects on shipping and leisure vessels, thus producing severe problems for marine and naval sectors due to corrosion with consequent elevated fuel consumption and higher maintenance costs. The development of anti-fouling or fouling release coatings creates deterrent surfaces that prevent the initial settlement of microorganisms. In this regard, new silica-based materials were prepared using two alkoxysilane cross-linkers containing epoxy and amine groups (i.

Functional Nanohybrids and Nanocomposites Development for the Removal of Environmental Pollutants and Bioremediation.

World population growth, with the consequent consumption of primary resources and production of waste, is progressively and seriously increasing the impact of anthropic activities on the environment and ecosystems. Environmental pollution deriving from anthropogenic activities is nowadays a serious problem that afflicts our planet and that cannot be neglected. In this regard, one of the most challenging tasks of the 21st century is to develop new eco-friendly, sustainable and economically-sound technologies to remediate the environment from pollutants.

Synthesis, Chemical-Physical Characterization, and Biomedical Applications of Functional Gold Nanoparticles: A Review.

Relevant properties of gold nanoparticles, such as stability and biocompatibility, together with their peculiar optical and electronic behavior, make them excellent candidates for medical and biological applications. This review describes the different approaches to the synthesis, surface modification, and characterization of gold nanoparticles (AuNPs) related to increasing their stability and available features useful for employment as drug delivery systems or in hyperthermia and photothermal therapy. The synthetic methods reported span from the well-known Turkevich synthesis, reduction with NaBH with or without citrate, seeding growth, ascorbic acid-based, green synthesis, and Brust-Schiffrin methods.

Photoinduced Water Oxidation in Chitosan Nanostructures Containing Covalently Linked Ru Chromophores and Encapsulated Iridium Oxide Nanoparticles.

The luminophore Ru(bpy) (dcbpy) (bpy=2,2'-bipyridine; dcbpy=4,4'-dicarboxy-2,2'-bipyridine) is covalently linked to a chitosan polymer; crosslinking by tripolyphosphate produced Ru-decorated chitosan fibers (NS-RuCh), with a 20 : 1 ratio between chitosan repeating units and Ru chromophores. The properties of the Ru compound are unperturbed by the chitosan structure, with NS-RuCh exhibiting the typical metal-to-ligand charge-transfer (MLCT) absorption and emission bands of Ru complexes. When crosslinks are made in the presence of IrO nanoparticles, such species are encapsulated within the nanofibers, thus generating the IrO ⊂NS-RuCh system, in which both Ru photosensitizers and IrO water oxidation catalysts are within the nanofiber structures.

Nanostructured Surface Finishing and Coatings: Functional Properties and Applications.

This review presents current literature on different nanocomposite coatings and surface finishing for textiles, and in particular this study has focused on smart materials, drug-delivery systems, industrial, antifouling and nano/ultrafiltration membrane coatings. Each of these nanostructured coatings shows interesting properties for different fields of application. In this review, particular attention is paid to the synthesis and the consequent physico-chemical characteristics of each coating and, therefore, to the different parameters that influence the substrate deposition process.

Photoinduced Charge Separation in a Donor-Spacer-Acceptor Dyad with N-Annulated Perylene Donor and Methylviologen Acceptor.

The first donor-acceptor species in which a strongly emissive N-annulated perylene dye is connected to a methylviologen electron acceptor unit via its macrocyclic nitrogen atom, is prepared by a stepwise, modular procedure. The absorption spectra, redox behavior, spectroelectrochemistry and photophysical properties of this dyad and of its model species are investigated, also by pump-probe fs transient absorption spectroscopy. Photoinduced oxidative electron transfer from the excited state of the dyad, centered on the N-annulated perylene subunit, to the appended methyviologen electron acceptor takes place in a few ps.

Absorption spectra, photophysical properties, and redox behavior of ruthenium(II) polypyridine complexes containing accessory dipyrromethene-BF2 chromophores.

The six multichromophoric species 1-6, containing the potentially luminescent Ru(II) polypyridine subunits and 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene fluorophores (dipyrromethene-BF(2) dyes, herein after called bodipy), have been prepared and their absorption spectra, luminescence properties (both at room temperature in fluid solution and at 77 K in rigid matrix), and redox properties have been investigated (for the structuralformulas of all the compounds, see Figure 1). For comparison purposes, also the same properties of the bodipy-based free ligands have been examined. Three of the multichromophoric species (1-3) are based on the Ru(bpy)(3)-type metal subunit, whereas 4-6 are based on the Ru(terpy)(2)-type metal subunit.

The elusive phosphorescence of pyrromethene-BF2 dyes revealed in new multicomponent species containing Ru(II)-terpyridine subunits.

The triplet emitting state of an indacene at 774 nm (of 50 ms life-time) was observed for the first time in new ruthenium(II) complexes based on bipartite ligands carrying one or two indacene subunits linked via phenylethynyl connectors to terpyridine fragments.

A new heptanuclear dendritic ruthenium(II) complex featuring photoinduced energy transfer across high-energy subunits.

The new heptanuclear ruthenium(II) dendron, [Cl(2)Ru{(micro-2,3dpp)Ru[(micro-2,3-dpp)Ru(bpy)2]2}2](PF6)12 (1; 2,3-dpp=2,3-bis(2'-pyridyl)pyrazine; bpy = 2,2'-bipyridine), was prepared by means of the "complexes as ligands/complexes as metals" synthetic strategy, and its absorption spectrum, redox behavior, and luminescence properties were investigated. Compound 1 is a multicomponent species, which contains three different types of chromophores (namely, the {Cl(2)Ru(micro-2,3-dpp)2} core, the {Ru(micro-2,3dpp)3}2+ intermediate, and the {(bpy)2Ru(micro-2,3-dpp)}2+ peripheral subunits) and several redox-active sites. The new species exhibits very intense absorption bands in the UV region (epsilon value in the 10(5)-10(6) M(-1) cm(-1) range) as a result of spin-allowed ligand-centered (LC) transitions, and intense bands in the visible region (epsilon value in the 10(4)-10(5) M(-1) cm(-1) range) as a result of the various spin-allowed metal-to-ligand charge-transfer (MLCT) transitions.