Aggregation-induced emission of cyclometalated rhodium(III) and iridium(III) phenylpyridine complexes with ancillary 1,3-diketones.

A joint structural and spectroscopic study of simple bis-cyclometataled rhodium(III) and iridium(III) complexes with 2-phenylpyridine and aromatic ß-diketones (dibenzoylmethane, benzoylacetone, benzoyltrifluoroacetone, and 2-thenoyltrifluoroacetone) reveals an interplay between the solid-state emission efficiency and crystal packing peculiarities of the complexes. Although the prepared rhodium(III) cyclometalates are isostructural with iridium(III) analogues, different types of π-π interactions are responsible for the aggregation-induced emission (AIE) of the complexes depending on the metal ion. For iridium(III) complexes, pyridyl-pyridyl contacts are essential for AIE because they lower the energy of the emissive metal-to-ligand charge transfer state below that of the non-emissive state located at the ancillary ligand. Enabled by phenyl-pyridyl interactions partially blocking the population of non-emissive d-d states, solid-state phosphorescence enhancement is successfully achieved in a rhodium(III) complex with ancillary benzoyltrifluoroacetone, which is the first example of a rhodium complex exhibiting AIE.

Rational design of efficient photosensitizers based on cyclometalated iridium(III) complexes with 2-arylbenzimidazole and aromatic 1,3-diketone ligands.

A judicious selection of substituents in cyclometalating 2-arylbenzimidazoles and an ancillary aromatic 1,3-diketone enabled the creation of heteroleptic iridium(III) complexes demonstrating strong light absorption up to 500 nm (ε ≈ 10 000-12 000 M-1 cm-1). The complexes, which were studied by various spectroscopic techniques, single-crystal X-ray diffraction and cyclic voltammetry, displayed tunable absorption maxima depending on the nature of substituents and their positions. The experimental study was corroborated by quantum chemical calculations, which showed an increased contribution of intraligand charge transfer transitions to the visible light absorption in the case of complexes containing electron-withdrawing substituents in the ligands. Despite being of high intensity, some of these transitions are responsible for the formation of the excited states located at large distances from the 'anchoring' fragment incorporated in the ancillary ligand. In turn, incorporation of electron-donating substituents at the para-position to the Ir-C bonds increases the number of excited states located on the ancillary ligand. The destabilization of the HOMO, which is caused by the increase in the electron-donating ability of the substituents in the metalated rings, translated into negative shifts of the Ir4+/Ir3+ redox potential, affecting, in some cases, the degree of electrochemical reversibility of the complexes. Several complexes having strong light-harvesting characteristics and undergoing reversible oxidation in the appropriate potential range were used for coating the TiO2 photoanodes, which reached an efficiency of 2.15% upon irradiation with the standard AM 1.5 spectrum.

Rewritable and Tunable Laser-Induced Optical Gratings in Phase-Change Material Films.

Laser-induced periodic surface structures (LIPSS) can be fabricated in virtually all types of solid materials and show great promise for efficient and scalable production of surface patterns with applications in various fields from photonics to engineering. While the majority of LIPSS manifest as modifications of the surface relief, in special cases, laser impact can also lead to periodic modulation of the material phase state. Here, we report on the fabrication of high-quality periodic structures in the films of phase-change material Ge2Sb2Te5 (GST). Due to considerable contrast of the refractive index of GST in its crystalline and amorphous states, the fabricated structures provide strong spatial modulation of the optical properties, which facilitates their applications. By changing the excitation laser wavelength, we observe the scaling of the grating period as well as transition between formation of different types of LIPSS. We optimize the laser exposure routine to achieve large-scale high-quality phase-change gratings with controllable period and demonstrate their reversible tunability through intermediate amorphization steps. Our results reveal the prospects of fast and rewritable fabrication of high-quality periodic structures for photonics and can serve as a guideline for further development of phase-change material-based optical elements.

Polydimethylsiloxane Elastomers Filled with Rod-Like α-MnO2 Nanoparticles: An Interplay of Structure and Electrorheological Performance.

For the first time, electroactive nanocomposite elastomers based on polydimethylsiloxane and filled with rod-like α-MnO2 nanoparticles have been obtained. The curing of the filled elastomer in an electric field, resulting in the ordering of the α-MnO2 particles, had a significant effect on the degree of polymer crosslinking, as well as on the electrorheological characteristics of the nanocomposites obtained through this process, namely the values of the storage and loss moduli. The dielectric spectra of filled elastomers in the frequency range 25-106 Hz were analysed in terms of interfacial relaxation processes. It has been shown, for the first time, that the application of an electric field leads to a decrease in the value of the Payne effect in composite elastomers. Analysis of the rheological effect in the obtained materials has demonstrated the possibility of designing highly efficient electrorheological elastomers that change their elastic properties by 4.3 times in electric fields of up to 2 kV/mm.

Cyclometalated Ru(II) complexes with tunable redox and optical properties for dye-sensitized solar cells.

Cyclometalated Ru(ii) complexes with 2-arylbenzimidazole antenna ligands bearing electron-donor/withdrawing substituents and anchoring 4,4'-dimethoxycarbonyl-2,2'-bipyridine have been prepared and their structure, optical and electrochemical properties have been studied. The complexes possess enhanced light-harvesting characteristics compared to those of the standard N719 dye and absorb light up to 750 nm. In addition, they demonstrate reversible redox behavior with Ru3+/Ru2+ potentials being finely tuned by the change of the electron-donating ability of cyclometalated ligands. After a mild hydrolysis of dimethoxycarbonyl groups the excellent optical properties of the complexes remain unchanged and they show good efficiency when tested in dye-sensitized solar cells.

Surfactant-Switched Positive/Negative Electrorheological Effect in Tungsten Oxide Suspensions.

The electrorheological (ER) effect was experimentally observed in dielectric suspensions containing tungsten oxide (WO3) modified with surfactant molecules (sodium dodecyl sulfate (SDS) and dodecylamine (DDA)) in electric fields up to several kilovolts per millimeter. The dielectric properties of WO3 suspensions in silicone oil were analyzed, depending on the frequency of the electric field, in the range from 25 to 106 Hz. Unmodified WO3 suspensions, as well as suspensions modified with sodium dodecyl sulfate, were shown to exhibit a positive electrorheological effect, whereas suspensions modified with dodecylamine demonstrated a negative electrorheological effect. The quantitative characteristics of the negative electrorheological effect in the strain-compression and shear regimes were obtained for the first time. Visualization experiments were performed to see the chain structures formed by WO3 particles modified with sodium dodecyl sulfate, as well as for dynamic electroconvection in electrorheological fluids containing WO3 modified with dodecylamine. The negative electrorheological effect was shown to be associated with the processes of phase separation in the electric field, which led to a multiplicative effect and a strong electroconvection of the suspension at field strengths above 1 kV/mm.

Synthesis, Photophysical and Redox Properties of the D-π-A Type Pyrimidine Dyes Bearing the 9-Phenyl-9H-Carbazole Moiety.

Novel donor-π-acceptor dyes bearing the pyrimidine unit as an electron-withdrawing group have been synthesized by using combination of two processes, based on the microwave-assisted Suzuki cross-coupling reaction and nucleophilic aromatic substitution of hydrogen. Spectral properties of the obtained dyes in six aprotic solvents of various polarities have been studied by ultraviolet-visible and fluorescence spectroscopy. In contrast to the absorption spectra, fluorescence emission spectra displayed a strong dependence from their solvent polarities. The nature of the observed long wavelength maxima has been elucidated by means of quantum chemical calculations. The electrochemical properties of these dyes have been investigated by using cyclic voltammetry, while their photovoltaic performance was evaluated by a device fabrication study. The experimental and calculation data show that all of the dyes can be regarded as potentially good photosensitizers for dye-sensitized solar cells.