Toward Rhenium-Based Circularly Polarized OLEDs Using Tailored Chiral Re(CO) Emitters.

Chiral rhenium(I) emitters exhibiting circularly polarized phosphorescence (CPP) are an attractive mainstay for CP organic light-emitting diodes (CP-OLEDs). However, the efficiency of such emitters is not ideal, and they have never been explored for circularly polarized electroluminescence (CPEL) applications. Here, we have tailored robust chiral Re(I) complexes with improved CPP properties, and demonstrated CPEL from rhenium emitters for the first time.

Coinage metal(I) clusters supported by a 1,10-phenanthroline-phosphine: orange-to-NIR phosphorescence, metallophilic interactions and enhanced cytotoxicity.

A series of small coinage metal(I) clusters has been selectively synthesized using 2-(diphenylphosphino)-1,10-phenanthroline (L), a new promising dimetal-binding -ligand (L). Its reaction with CuI yields the complex [CuL(μ-I)][CuI], while the treatment of L with Au(tht)Cl/Ag or Au(tht)Cl/Cu systems leads to the assembly of [AuAgLCl], [AuCuLCl], [CuAuL] and [AgAuL] clusters. Theoretical analysis revealed pronounced intermetallic close shell interactions in these di- and trinuclear ensembles.

Outstanding Circularly Polarized TADF in Chiral Cu(I) Emitters: From Design to Application in CP-TADF OLEDs.

Low-cost molecular emitters that merge circularly polarized luminescence (CPL) and thermally activated delayed fluorescence (TADF) properties are attractive for many high-tech applications. However, the design of such emitters remains a difficult task. To address this challenge, here, we propose a simple and efficient strategy, demonstrated by the design of pseudochiral-at-metal complexes [Cu(L*)DPEPhos]PF bearing a (+)/(-)-menthol-derived 1,10-phenanthroline ligand (L*).

Fast and reversible solvent-vapor-induced 1D to 2D transformation in emissive Ag(I)-organic networks.

We report here an unprecedentedly fast and reversible transformation between 1D and 2D MOFs/CPs induced through organic solvent vapours. The transformations occur at room temperature in just 15-20 min, accompanied by a significant change in the observed phosphorescence. These findings provide a new insight into the design of luminescent networks with stimuli-switchable dimensionality.

Synthesis, Structure, and Magnetic and Biological Properties of Copper(II) Complexes with 1,3,4-Thiadiazole Derivatives.

New coordination compounds of copper(II) with 2,5-bis(ethylthio)-1,3,4-thiadiazole (L) and 2,5-bis(pyridylmethylthio)-1,3,4-thiadiazole (L) with compositions Cu(L)Br, Cu(L)(CN), Cu(L)Cl, and Cu(L)Br were prepared. The complexes were identified and studied by CHN analysis, infrared (IR) spectroscopy, powder X-Ray diffraction (XRD), and static magnetic susceptibility. The crystal structures of Cu(II) complexes with L were determined.

Strong Magnetically-Responsive Circularly Polarized Phosphorescence and X-Ray Scintillation in Ultrarobust Mn(II)-Organic Helical Chains.

Over recent years, Mn(II)-organic materials showing circularly polarized luminescence (CPL) have attracted great interest because of their eco-friendliness, cheapness, and room temperature phosphorescence. Using the helicity design strategy, herein, chiral Mn(II)-organic helical polymers are constructed featuring long-lived circularly polarized phosphorescence with exceptionally high g and Φ magnitudes of 0.021% and 89%, respectively, while remaining ultrarobust toward humidity, temperature, and X-rays.

Recent progress in dichalcophosphate coinage metal clusters and superatoms.

Atomically precise clusters of group 11 metals (Cu, Ag, and Au) attract considerable attention owing to their remarkable structure and fascinating properties. One of the unique subclasses of these clusters is based on dichalcophosphate ligands of [(RO)PE] type (E = S or Se, and R = alkyl). These ligands successfully stabilise the most diverse Cu, Ag, and Au clusters and superatoms, spanning from simple ones to amazing assemblies featuring unusual structural and bonding patterns.

TADF and X-ray Radioluminescence of New Cu(I) Halide Complexes: Different Halide Effects on These Processes.

A series of complexes [CuX(PicPO)] (X = Cl, Br, I) based on tris(pyridin-2-ylmethyl)phosphine oxide (PicPO) has been synthesized. At 298 K, these compounds exhibit thermally activated delayed fluorescence (TADF) of (M+X)LCT type with λ varying from 485 to 545 nm, and quantum efficiency up to 54%. In the TADF process, the halide effect appears as the emission intensification and bathochromic shift of λ in the following order X = I < Br < Cl.

A family of CuI-based 1D polymers showing colorful short-lived TADF and phosphorescence induced by photo- and X-ray irradiation.

Exploiting 2-(alkylsulfonyl)pyridines as 1,3-N,S-ligands, herein we have constructed 1D CuI-based coordination polymers (CPs) bearing unprecedented (CuI) chains and possessing remarkable photophysical properties. At room temperature, these CPs show efficient TADF, phosphorescence or dual emission in the deep-blue to red range with outstandingly short decay times of 0.4-2.

A new subclass of copper(I) hybrid emitters showing TADF with near-unity quantum yields and a strong solvatochromic effect.

We introduce here a new subclass of copper(I) hybrid emitters simultaneously containing [CuI] anions and Cu cations, separated in space by a Janus head ligand. When UV-irradiated at 298 K, these unique "Two-In-One" hybrids exhibit a short-lived green TADF with near-unity quantum yield and a strong solvatochromic effect. Moreover, they manifest a strong radioluminescence upon X-ray irradiation.

Combined modelling of mRNA decay dynamics and single-molecule imaging in the Drosophila embryo uncovers a role for P-bodies in 5' to 3' degradation.

Regulation of mRNA degradation is critical for a diverse array of cellular processes and developmental cell fate decisions. Many methods for determining mRNA half-lives rely on transcriptional inhibition or metabolic labelling. Here, we use a non-invasive method for estimating half-lives for hundreds of mRNAs in the early Drosophila embryo.

Halogen Bonding Channels for Magnetic Exchange in Cu(II) Complexes with 2,5-Di(methylthio)-1,3,4-thiadiazole.

Copper(II) complexes with 2,5-bis(methylthio)-1,3,4-thiadiazole (tda) formulated as [Cu(tda) X ] (n=2, X=Cl , Br , C N ; n= 1, X=C N ) have been isolated and fully characterized. The crystal structures of all compounds have been determined using single-crystal X-ray diffraction (SCXRD). A study of the magnetic susceptibility in the range 1.

Tris(2-Pyridyl)Arsine as a New Platform for Design of Luminescent Cu(I) and Ag(I) Complexes.

The coordination behavior of tris(2-pyridyl)arsine (PyAs) has been studied for the first time on the example of the reactions with CuI, CuBr and AgClO. When treated with CuI in CHCl medium, PyAs unexpectedly affords the scorpionate complex [Cu(PyAs)I]∙CHCl only, while this reaction in MeCN selectively leads to the dimer [Cu(PyAs)I]. At the same time, the interaction of CuBr with PyAs exclusively gives the dimer [Cu(PyAs)Br].

Trigonal Planar Au@Ag Clusters Showing Exceptionally Fast and Efficient Phosphorescence in Violet to Deep-Blue Region.

We report here a series of original ligand-supported trigonal planar Au@Ag clusters exhibiting bright solid-state phosphorescence in violet to deep-blue range (λ =410-442 nm) with remarkably short decay times (0.36-1.36 μs) and up to 96 % emission quantum yield at 298 K.

Controllable Synthesis and Luminescence Behavior of Tetrahedral Au@Cu and Au@Ag Clusters Supported by tris(2-Pyridyl)phosphine.

We report herein a family of polynuclear complexes, [Au@Ag(PyP)]X and [Au@Cu(PyP)]X [X = NO, ClO, OTf, BF, SbF], containing unprecedented Au-centered Ag and Cu tetrahedral cores supported by tris(2-pyridyl)phosphine (PyP) ligands. The [Au@Ag] clusters are synthesized controlled substitution of the central Ag(I) ion in all-silver [Ag@Ag] precursors by the reaction with Au()Cl, while the [Au@Cu] cluster is assembled through the treatment of a pre-organized [Au(PyP)] metallo-ligand with 4 equiv of a Cu(I) source. The structure of the Au@M clusters has been experimentally and theoretically investigated to reveal very weak intermolecular Au-M metallophilic interactions.

New Approach toward Dual-Emissive Organic-Inorganic Hybrids by Integrating Mn(II) and Cu(I) Emission Centers in Ionic Crystals.

Inorganic-organic hybrid luminescent materials have received great attention for their potential applications in a wide range of clean/renewable energy-related areas, including photovoltaics and solid-state lighting. Herein, we present a unique and general "Mn + Cu" approach by blending two earth-abundant luminogenic metals, manganese and copper, within a single ionic structure to construct a remarkable family of low-cost and multifunctional hybrid materials featuring dual emission, as well as triboluminescence and second-harmonic generation response. The novel hybrid materials are made of diphosphine dioxide-chelated [Mn(O∧O)] cations and various anionic [CuI] clusters, ensuring manifestation of dual phosphorescence streamed from octahedral Mn ions (605-648 nm) and iodocuprate anions (480-728 nm).

The Association of Microbiome Dysbiosis With Colorectal Cancer.

Many studies have been conducted to identify the causative organisms in colorectal cancer (CRC) and compare the microbiota of healthy individuals and those with CRC. The pathways by which the microbiota promotes CRC development are not yet fully understood. The hypothesized mechanisms include damage to the DNA, production of carcinogenic metabolites, and promotion of chronic inflammation.

Pyridylarsine-based Cu(I) complexes showing TADF mixed with fast phosphorescence: a speeding-up emission rate using arsine ligands.

Can arsine ligands be preferred over similar phosphines to design Cu(I)-based TADF materials? The present study reveals that arsines can indeed be superior to reach shorter decay times of Cu(I) emitters. This has been exemplified on a series of bis(2-pyridyl)phenylarsine-based complexes [Cu(PyAsPh)X] (X = Cl, Br, and I), the emission decay times of which are significantly shorter (2-9 μs at 300 K) than those of their phosphine analogs [Cu(PyPPh)X] (5-33 μs). This effect is caused by two factors: (i) large Δ(S-T) gaps of the arsine complexes (1100-1345 cm), thereby phosphorescence is admixed with TADF at 300 K, thus reducing the total emission decay time compared to the TADF-only process by 5-28%; (ii) higher SOC strength of arsenic ( = 1202 cm) against phosphorus ( = 230 cm) makes the (T → S) rate of the Cu(I)-arsine complexes by 1.

Coordination-induced emission enhancement in copper(I) iodide coordination polymers supported by 2-(alkylsulfanyl)pyrimidines.

First examples of copper(i) complexes with 2-(alkylsulfanyl)pyrimidine ligands have been synthesized. Reactions of copper(i) iodide with 2-(methylsulfanyl)pyrimidine (L1) in various metal-to-ligand molar ratios in MeCN afford a ladder-type coordination polymer [Cu2L1I2]n with polymeric chains built from double-stranded (Cu2I2)n ribbons supported on both sides by μ2-N,S-L1 molecules. Although the second ligand, 2-(ethylsulfanyl)pyrimidine (L2), differs from L1 only by a methylene group, its reactions with copper(i) iodide in MeCN yield not only a congenerous coordination polymer, [Cu2L2I2]n, but also [CuL2I]n, in which a similar (Cu2I2)n ribbon is decorated by N-monodentate L2 molecules.

Selenium Nanocomposites in Natural Matrices as Potato Recovery Agent.

The paper presents a study of the effect of chemically synthesized selenium nanocomposites (Se NCs) in natural polymer matrices arabinogalactan (AG) and starch (ST) on the viability of the potato ring rot pathogen (), potato plants in vitro, and the soil bacterium . It was found that the studied Se NCs have an antibacterial effect against the phytopathogenic , reducing its growth rate and ability to form biofilms. It was revealed that Se NC based on AG (Se/AG NC) stimulated the growth and development of potato plants in vitro as well as their root formation.

Silver(I)-Organic Frameworks Showing Remarkable Thermo-, Solvato- And Vapochromic Phosphorescence As Well As Reversible Solvent-Driven 3D-to-0D Transformations.

A series of isoreticular Ag(I) luminescent metal-organic frameworks (LMOFs), {[AgL(CHCN)](X)} (X = ClO, OTf, and BF), has been designed, exploiting diphenyl(2-pyrazyl)phosphine (L) as a multidentate linker. At ambient temperature, these compounds emit a bright long-lived phosphorescence (λ = 545-555 nm) with a quantum efficiency as high as 22%, which is the highest value for phosphorescent Ag-LMOFs. The prepared LMOFs also exhibit pronounced thermochromic luminescence, reversibly changing their emission color in the 300-77 K range.

Beyond Classical Coordination Chemistry: The First Case of a Triply Bridging Phosphine Ligand.

The first example of a triply bridging (μ -P) phosphine ligand has been discovered in the crown-shaped [Cu (μ -Hal) L] (Hal=Cl, Br, or I) complexes supported by tris[2-(2-pyridyl)ethyl]phosphine (L). Theoretical analysis completely confirms the observed μ -P-bridging pattern, revealing the interaction of the same lone pair of phosphorus with three valence 4s-orbitals of Cu atoms. The presented complexes exhibit outstanding blue phosphorescence (λ =442-465 nm) with the quantum efficiency reaching 100 %.

Dicopper(I) Paddle-Wheel Complexes with Thermally Activated Delayed Fluorescence Adjusted by Ancillary Ligands.

A suite of paddle-wheel shaped [Cu(PymPPh)(L)](PF) complexes showing efficient thermally activated delayed fluorescence (TADF) has been synthesized. In these complexes, Cu(I) ions are ,-bridged by three diphenyl(2-pyrimidyl)phosphine (PymPPh, L) ligands in a "head-to-tail" fashion, and one or both metals are also capped by the ancillary ligand (L = MeOH, MeCO, MeCN, PhCN). At ambient temperature, the solid complexes emit TADF with the quantum yield of up to 85% and the lifetimes of from 9.

Measurement of single-crystal piezo modulus by the method of diffraction of synchrotron radiation at angles near π.

This article presents measurements of the piezoelectric modulus of a single crystal of lanthanum gallium silicate (LGS, LaGaSiO). The piezoelectric modulus was measured by X-ray diffraction at angles close to backscattering. Experiments in such schemes are very sensitive to relative changes in the lattice constant in crystals caused by external influences (constant or alternating electric field, mechanical load, temperature change .