Rb[Li5Si2O7] – A Latecomer in the Family of Alkali Lithosilicates Hiding a Green-Emitting Lithosilicate

In order to expand the field of alkali lithosilicates, a new representative of the substance class with a previously unknown structure type was found based on solid-state synthesis. The novel compound with the sum formula Rb[Li₅Si₂O₇] crystallizes in the orthorhombic space group Pbcm (no. 57) with a=7.6269(3), b=9.5415(4), and c=9.4095(3) Å by means of single-crystal X-ray diffraction. The structure consists of a highly condensed lithosilicate framework, built up of corner- and edge-linked [LiO₄]-tetrahedra and [Si₂O₇]-units, and the rubidium ions aligned in channels. Suitable crystals of the material were obtained using sealed tantalum ampoules as reaction tube at a temperature of 750 °C. The new compound was further characterized via powder diffraction, Rietveld analysis, and EDX measurements. At first glance, Eu²⁺-doped Rb[Li₅Si₂O₇] reveals an intense green luminescence. In-depth crystal analysis shows that a core-shell formation is present even for apparently high quality single-crystals. As a minority phase, the known green phosphor RbLi[Li₃SiO₄]₂:Eu²⁺ is the origin of the luminescence, representing a tiny core inside of the particles surrounded by a large matrix of transparent Rb[Li₅Si₂O₇] dominating the single-crystal diffraction pattern.     

Efficient Solar Cells Sensitized by Porphyrins with an Extended Conjugation Framework and a Carbazole Donor: From Molecular Design to Cosensitization

Porphyrin dyes containing the carbazole electron donor have been designed and optimized by wrapping the porphyrin framework, introducing an additional ethynylene bridge to extend the wavelength range of light absorption, and further suppression of the dye aggregation by introducing additional alkoxy chains. Application of a cosensitization approach results in improved current density (J_sc) and open‐circuit voltage (V_oc) values, thus achieving the highest cell efficiency of 10.45 %. This work provides an effective combined strategy of molecular design and cosensitization for developing efficient dye‐sensitized solar cells (DSSCs). In addition, carbazole has been demonstrated to be a promising donor for porphyrin sensitizers.     

Sterically Shielded Heptamethine Cyanine Dyes for Bioconjugation and High Performance Near‐Infrared Fluorescence Imaging

The near‐infrared window of fluorescent heptamethine cyanine dyes greatly facilitates biological imaging because there is deep penetration of the light and negligible background fluorescence. However, dye instability, aggregation, and poor pharmacokinetics are current drawbacks that limit performance and the scope of possible applications. All these limitations are simultaneously overcome with a new molecular design strategy that produces a charge balanced and sterically shielded fluorochrome. The key design feature is a meso‐aryl group that simultaneously projects two shielding arms directly over each face of a linear heptamethine polyene. Cell and mouse imaging experiments compared a shielded heptamethine cyanine dye (and several peptide and antibody bioconjugates) to benchmark heptamethine dyes and found that the shielded systems possess an unsurpassed combination of photophysical, physiochemical, and biodistribution properties that greatly enhance bioimaging performance.     

Graphene-Oxide-Based Fluoro- and Chromo-Genic Materials and Their Applications

Composite materials and their applications constitute a hot field of research nowadays due to the fact that they comprise a combination of the unique properties of each component of which they consist. Very often, they exhibit better performance and properties compared to their combined building blocks. Graphene oxide (GO), as the most widely used derivative of graphene, has attracted widespread attention because of its excellent properties. Abundant oxygen-containing functional groups on GO can provide various reactive sites for chemical modification or functionalization of GO, which in turn can be used to develop novel GO-based composites. This review outlines the most recent advances in the field of novel dyes and pigments encompassing GO as a key ingredient or as an important cofactor. The interactions of graphene with other materials/compounds are highlighted. The special structure and unique properties of GO have a great effect on the performance of fabricated hybrid dyes and pigments by enhancing the color performance of dyes, the anticorrosion properties of pigments, the viscosity and rheology of inks, etc., which further expands the applications of dyes and pigments in dyeing, optical elements, solar-thermal energy storage, sensing, coatings, and microelectronics devices. Finally, challenges in the current development as well as the future prospects of GO-based dyes and pigments are also discussed. This review provides a reference for the further exploration of novel dyes and pigments.     

Chemometric Tools to Point Out Benchmarks and Chromophores in Pigments through Spectroscopic Data Analyses

Spectral preprocessing data and chemometric tools are analytical methods widely applied in several scientific contexts i.e., in archaeometric applications. A systematic classification of natural powdered pigments of organic and inorganic nature through Principal Component Analysis with a multi-instruments spectroscopic study is presented here. The methodology allows the access to elementary and molecular unique benchmarks to guide and speed up the identification of an unknown pigment and its recipe. This study is conducted on a set of 48 powdered pigments and tested on a real-case sample from the wall painting in S. Maria Delle Palate di Tusa (Messina, Italy). Four spectroscopic techniques (X-ray Fluorescence, Raman, Attenuated Total Reflectance and Total Reflectance Infrared Spectroscopies) and six different spectrometers are tested to evaluate the impact of different setups. The novelty of the work is to use a systematic approach on this initial dataset using the entire spectroscopic energy range without any windows selection to solve problems linked with the manipulation of large analytes/materials to find an indistinct property of one or more spectral bands opening new frontiers in the dataset spectroscopic analyses.     

Study on Phase-Formation Mechanism and Intergrowth for Bi(Pb)-Sr-Ca-Cu-O System

In this paper, the phase-formation mechanism of Bi-based superconductors was systematically investigated by using high-temperature X-ray diffraction, differential thermal analysis (DTA) and crystallization of amorphous state. The transformations among Bi-based 2201, 2212 and 2223 phases were observed, and the intergrown phenomenon of the 2201, 2212 and 2223 phases was explained. It was proposed that there exist a composition equilibrium between 2212 phase and Ca2CuO3 and a competition of thermody-namic stability among Ca2CuO3, 2212 and 2223 phases. This is why it is difficult to prepare the 2223 phase. After Pb was doped in Bi-Sr-Ca-Cu-O system, Ca2CuO3 phase in the Bi-Sr-Ca-Cu-O system was replaced by Ca2PbO4, so that the composition equilibrium and competition of thermodynamic stability mentioned above were avoided.     

Revealing Phosphorus Nitrides up to the Megabar Regime: Synthesis of α′-P3N5, δ-P3N5 and PN2

Non-metal nitrides are an exciting field of chemistry, featuring a significant number of compounds that can possess outstanding material properties. These properties mainly rely on maximizing the number of strong covalent bonds, with crosslinked XN₆ octahedra frameworks being particularly attractive. In this study, the phosphorus–nitrogen system was studied up to 137 GPa in laser-heated diamond anvil cells, and three previously unobserved phases were synthesized and characterized by single-crystal X-ray diffraction, Raman spectroscopy measurements and density functional theory calculations. δ-P₃N₅ and PN₂ were found to form at 72 and 134 GPa, respectively, and both feature dense 3D networks of the so far elusive PN₆ units. The two compounds are ultra-incompressible, having a bulk modulus of K₀=322 GPa for δ-P₃N₅ and 339 GPa for PN₂. Upon decompression below 7 GPa, δ-P₃N₅ undergoes a transformation into a novel α′-P₃N₅ solid, stable at ambient conditions, that has a unique structure type based on PN₄ tetrahedra. The formation of α′-P₃N₅ underlines that a phase space otherwise inaccessible can be explored through materials formed under high pressure.     

BODIPY‐Bridged Push–Pull Chromophores for Nonlinear Optical Applications

A set of linear and dissymmetric BODIPY‐bridged push–pull dyes are synthesized. The electron‐donating substituents are anisole and dialkylanilino groups. The strongly electron‐accepting moiety, a 1,1,4,4‐tetracyanobuta‐1,3‐diene (TCBD) group, is obtained by insertion of an electron‐rich ethyne into tetracyanoethylene. A nonlinear push–pull system is developed with a donor at the 5‐position of the BODIPY core and the acceptor at the 2‐position. All dyes are fully characterized and their electrochemical, linear and nonlinear optical properties are discussed. The linear optical properties of dialkylamino compounds show strong solvatochromic behavior and undergo drastic changes upon protonation. The strong push–pull systems are non‐fluorescent and the TCBD‐BODIPY dyes show diverse photochemistry and electrochemistry, with several reversible reduction waves for the tetracyanobutadiene moiety. The hyperpolarizability μβ of selected compounds is evaluated using the electric‐field‐induced second‐harmonic generation technique. Two of the TCBD‐BODIPY dyes show particularly high μβ (1.907 μm) values of 2050×10^?48 and 5900×10^?48 esu. In addition, one of these dyes shows a high NLO contrast upon protonation–deprotonation of the donor residue.     

Studies of heterogeneity properties of selected high-temperature superconductor surfaces

Nitrogen adsorption measured at 77 K was used to characterize the surface heterogeneity of high-temperature superconductor surfaces. Properties relating to adsorption and porosity of the solids (adsorption capacity, specific surface area, radii and volume of the pores, pore-size distribution function) were determined from nitrogen adsorption–desorption isotherms and atomic force microscopy (AFM) for a series of oxide superconductors. It is shown that the adsorption isotherms of all samples are S-shaped and belong to type II according to the IUPAC classification. On the basis of the nitrogen adsorption isotherms and AFM data, fractal dimensions were determined and correlations found with adsorption and porosity parameters.