Interstitial and substitutional doping of Mn in 2D PEAPbBr and BAPbBr perovskites.

Mn doping imposes intriguing optoelectronic properties on lead-halide perovskites; however, its impact on their crystal structure remains unclear. This study investigates the consequences of interstitial and substitutional Mn doping on the lattice-strain and interplanar spacings of 2D perovskites and correlates the structural changes to their optical properties.

Synthesis and Characterization of Symmetrical -Heterocyclic Carbene Copper(II) Complexes-An Investigation of the Influence of Pyridinyl Substituents.

Three new tridentate copper(II) -heterocyclic carbene (NHC) complexes have been obtained and characterized with symmetrical C-4 substitutions on their pendent pyridine rings. Substitutions including methyl (Me), methoxy (OMe), and chloro (Cl) groups, which extend the library pincer Cu-NHC complexes under investigation, modify the impact of pyridinyl basicity on NCN pincer complexes. Both ligand precursors and copper(II) complexes are characterized using a range of techniques, including nuclear magnetic resonance (NMR) spectroscopy for H, C, P, and F nuclei, electrospray ionization mass spectrometry (ESI-MS), X-ray crystallography, cyclic voltammetry, and UV-Vis spectroscopy.

Photocatalytic Hydrogen Production with A Molecular Cobalt Complex in Alkaline Aqueous Solutions.

The thermodynamic favorability of an alkaline solution for the oxidation of water suggests the need for developing hydrogen evolution reaction (HER) catalysts that can function in basic aqueous solutions so that both of the half reactions in overall water splitting can occur in mutually compatible solutions. Although photocatalytic HERs have been reported mostly in acidic solutions and a few at basic pHs in mixed organic aqueous solutions, visible-light driven HER catalyzed by molecular metal complexes in purely alkaline aqueous solutions remains largely unexplored. Here, we report a new cobalt complex with a tetrapyridylamine ligand that catalyzes photolytic HER with turnover number up to 218 000 in purely aqueous solutions at pH 9.

Aminoquinoline-Based Tridentate ()-Copper Catalyst for C-N Bond-Forming Reactions from Aniline and Diazo Compounds.

A new tridentate Cu complex based on ()-1-(pyridin-2-yl)--(quinolin-8-yl)methanimine (PQM) was generated and characterized to support the activation of diazo compounds for the formation of new C-N bonds. This neutral Schiff base ligand was structurally characterized to coordinate with copper(II) in an equatorial fashion, yielding a distorted octahedral complex. Upon characterization, this copper(II) complex was used to catalyze an efficient and cost-effective protocol for C-N bond formation between -nucleophiles and copper carbene complexes arising from the activation of diazo carbonyl compounds.

Three water-soluble copper(II) -heterocyclic carbene complexes: toward copper-catalyzed ketone reduction under sustainable conditions.

A series of tridentate copper(II) -heterocyclic carbene (NHC) complexes with imidazole, benzimidazole, and 5,6-dimethylbenzimidazole azole rings were synthesized and comprehensively characterized X-ray crystallography, ESI-MS, cyclic voltammetry, and UV-Vis and EPR spectroscopic studies. These complexes were then utilized for the optimization of ketone reduction under sustainable conditions using 2-acetylpyridine and phenylsilane. The relationships between product formation, temperature, reaction time, and catalyst loading for the hydrogenation reactions are covered in detail.

Synthesis of -Fused Polycyclic Indole Derivatives via Ru(II)-Catalyzed C-H Bond Activation and Intramolecular Hydroarylation.

A new synthesis of -fused tetracyclic indole derivatives and their related polycyclic analogues has been developed based on ruthenium(II)-catalyzed C-H activation and intramolecular hydroarylation. A series of polycyclic indoles with a 3-formyl group have been prepared in good to high yields. Various aliphatic and aromatic amines have been studied to form a transient directing group with the aldehyde for the catalytic process.

Synthesis and Characterization of Bipyridyl-(Imidazole) Mn(II) Compounds and Their Evaluation as Potential Precatalysts for Water Oxidation.

Metalloenzymes make extensive use of manganese centers for oxidative catalysis, including water oxidation; the need to develop improved synthetic catalysts for these processes has long motivated the development of bioinspired manganese complexes. Herein, we report a series of bpy-(imidazole) (n = 1 or 2) (bpy = 2,2'-bipyridyl) ligands and their Mn complexes. Four Mn complexes are structurally characterized using single-crystal X-ray diffraction, revealing different tridentate and tetradentate ligand coordination modes.

Unexpected alkyl isomerization at the silicon ligand of an unsaturated Rh complex: combined experiment and theory.

The formation of dimer [(μ-Cl)Rh-((,,)PhP(-CHCHSiPr)(-CHCHSiPrPr))] (Rh-3) with an -propyl group on one of the silicon atoms as a minor product was affected by the reaction of [RhCl(COD)] with proligand PhP(-CHCHSiHPr), L1. The major product of the reaction was monomeric 14-electron Rh(III) complex [ClRh((,,)PhP(-CHCHSiPr))] (Rh-1). Computations revealed that the monomer-dimer equilibrium is shifted toward the monomer with four isopropyl substituents on the two Si atoms of the ligand as in Rh-1; conversely, the dimer is favored with only one -propyl as in Rh-3, and with less bulky alkyl substituents such as in [ClRh((,,)PhP(-CHCHSiMe)] (Rh-2).

Copper complexes for the chemoselective -arylation of arylamines and sulfanilamides Chan-Evans-Lam cross-coupling.

Copper(II) complexes with tridentate -ligands were utilized for Chan-Evans-Lam (CEL) cross-coupling reactions to enable the -arylation of multifarious -nucleophiles through the activation of aryl boronic acids. A condition-specific methodology was developed to chemoselectively target the amine sulfonamide -arylation of 4-aminobenzenesulfonamide using new catalysts. Two different pyridine-based ligands and corresponding copper(II) complexes were characterized using H and C-NMR, FTIR, and UV-vis spectroscopy, HRMS, single-crystal X-ray diffraction, and cyclic voltammetry.

Homogeneous MOF-supported catalysis: a direct comparison of catalytic hydroboration with Ni tripodal PE (E = Si, Ge) complexes.

The MOF material NU-1000 was employed to host Ni tripodal complexes prepared from new organometallic precursors [HNi((,,,)-E(-CHCHPPh)], E = Si (Ni-1), Ge (Ni-2). The new heterogeneous catalytic materials, Ni-1@NU-1000 and Ni-2@NU-1000, show the advantages of both homogeneous and heterogeneous catalysts. They catalyze the hydroboration of aldehydes and ketones more efficiently than the homogeneous Ni-1 and Ni-2, under aerobic conditions and show recyclability.

Steric Effects on the Chelation of Mn and Zn by Hexadentate Polyimidazole Ligands: Modeling Metal Binding by Calprotectin Site 2.

Recently, there has been increasing interest in the design of ligands that bind Mn with high affinity and selectivity, but this remains a difficult challenge. It has been proposed that the cavity size of the binding pocket is a critical factor in most synthetic and biological examples of selective Mn binding. Here, we use a bioinspired approach adapted from the hexahistidine binding site of the manganese-sequestering protein calprotectin to systematically study the effect of cavity size on Mn and Zn binding.

Effects of electron-donating ability of binding sites on coordination number: the interactions of a cyclic Schiff base with copper ions.

The stepwise addition of Cu ions to the nonplanar cyclic Schiff base 5,9,14,18-tetramethyl-1,4,10,13-tetraazacyclooctadeca-5,8,14,17-tetraene-7,16-dione (Hdaaden, CHNO), yields a one-end-open dinuclear copper chelate. The pyridine adduct of the dinuclear copper chelate, namely, [μ-6,11-dimethyl-7,10-diazahexadeca-5,11-diene-2,4,13,15-tetraolato(4-)](pyridine)dicopper(II), [Cu(CHNO)(CHN)], was characterized by single-crystal X-ray crystallography. The two Cu atoms of the copper chelate display different coordination modes, i.

Tuning of Cu-Al Interactions in Complexes Derived from Tris(pyridonyl-6-methyl)aluminum Metalloligands.

A series of bioinspired polar atrane Cu-Al complexes were studied with a combined experimental and computational approach to assess the range and nature of Cu-Al interactions in these novel species. The aluminum metalloligand [Na{MeAl(OPy-6-Me)}] () was furnished in excellent yield (92%) from the nucleophilic attack of Na(OPy-6-Me) to AlMe and the subsequent alkane elimination reaction with 6-methyl-2-hydroxypyridine. At the same time, the metalloligand [Al(OPy-6-Me)] () was isolated in an also excellent yield (95%) via alkane elimination of AlMe with 6-methyl-2-hydroxypyridine.

Copper(II) NHC Catalyst for the Formation of Phenol from Arylboronic Acid.

Arylboronic acids are commonly used in modern organic chemistry to form new C-C and C-heteroatom bonds. These activated organic synthons show reactivity with heteroatoms in a range of substrates under ambient oxidative conditions. This broad reactivity has limited their use in protic, renewable solvents like water, ethanol, and methanol.

Barium and titanium dithiocarbamates as precursors for colloidal nanocrystals of emerging optoelectronic materials.

The synthesis and structures of ,-dialkyldithiocarbamate complexes of barium are reported; the compounds crystallize as one-dimensional coordination polymers. In combination with a titanium dithiocarbamate precursor, the compounds are demonstrated as competent single-source precursors for the solution-based preparation of colloidal BaTiS nanorods.

14-Electron Rh and Ir silylphosphine complexes and their catalytic activity in alkene functionalization with hydrosilanes.

Herein we report an experimental and computational study of a family of four coordinated 14-electron complexes of Rh(iii) devoid of agostic interactions. The complexes [X-Rh(κ(P,Si,Si)PhP(o-CHCHSiPr)], where X = Cl (Rh-1), Br (Rh-2), I (Rh-3), OTf (Rh-4), Cl·GaCl (Rh-5); derive from a bis(silyl)-o-tolylphosphine with isopropyl substituents on the Si atoms. All five complexes display a sawhorse geometry around Rh and exhibit similar spectroscopic and structural properties.

Functionalized NU-1000 with an Iridium Organometallic Fragment: SO Capture Enhancement.

A new material, MOF-type [Ir]@NU-1000, was accessed from the incorporation of the iridium organometallic fragment [Ir{κ(P,Si,Si)PhP(-CHCHSiPr)}] into NU-1000. The new material incorporates less than 1 wt % of Ir(III) (molar ratio Ir to NU-1000, 1:11), but the heat of adsorption for SO is significantly enhanced with respect to that of NU-1000. Being a highly promising adsorbent for SO capture, [Ir]@NU-1000 combines exceptional SO uptake at room temperature and outstanding cyclability.

INVICTUS: Intravitreal anti-VEGF and dexamethasone implant comparison for the treatment of diabetic macular edema: A 12 months follow-up study.

Purpose: To compare the efficacy of intravitreal injections (IVI) of ranibizumab (Lucentis, Novartis, Basel, Switzerland; RAN), aflibercept (Eylea, Bayer, Leverkusen, Germany; AFL) and dexamethasone implant (Ozurdex, Allergan, Irvine, California; DXI) in the treatment of naive diabetic macular oedema (DME) during a 12-month follow-up, in real life.

Methods: Nineteen eyes treated with RAN, 20 with AFL and 21 with DXI were analysed from inclusion up to 12 months (M12) with intermediate analysis at M6. Best corrected visual acuity (BCVA), fundus and central retinal thickness (CRT) using spectral-domain optical coherence tomography (SD-OCT; Spectralis/HRA, Heidelberg Engineering, Germany) were performed at inclusion, M3, M6 and M12.

Enhanced Hydrogen Evolution in Neutral Water Catalyzed by a Cobalt Complex with a Softer Polypyridyl Ligand.

To explore the structure-function relationships of cobalt complexes in the catalytic hydrogen evolution reaction (HER), we studied the substitution of a tertiary amine with a softer pyridine group and the inclusion of a conjugated bpy unit in a Co complex with a new pentadentate ligand, 6-[6-(1,1-di-pyridin-2-yl-ethyl)-pyridin-2-ylmethyl]-[2,2']bipyridinyl (Py3Me-Bpy). These modifications resulted in significantly improved stability and activity in both electro- and photocatalytic HER in neutral water. [Co(Py3Me-Bpy)(OH )](PF ) catalyzes the electrolytic HER at -1.

Scleral fixated intraocular lens by a modified technique: Methods and results.

Purpose: A certain number of conditions can result in compromised anterior and/or posterior capsular integrity. Several surgical options have been employed for repositioning dislocated intraocular lenses in the absence of adequate capsular support. The purpose of this study is to assess the functional outcomes and complication profile of a modified surgical technique for replacing dislocated intraocular lenses.

Room temperature magnetoelectric coupling in a molecular ferroelectric ytterbium(III) complex.

Magnetoelectric (ME) materials combine magnetic and electric polarizabilities in the same phase, offering a basis for developing high-density data storage and spintronic or low-consumption devices owing to the possibility of triggering one property with the other. Such applications require strong interaction between the constitutive properties, a criterion that is rarely met in classical inorganic ME materials at room temperature. We provide evidence of a strong ME coupling in a paramagnetic ferroelectric lanthanide coordination complex with magnetostrictive phenomenon.

Ruthenium-Catalyzed Enantioselective C-H Functionalization: A Practical Access to Optically Active Indoline Derivatives.

Ru(II)-catalyzed enantioselective C-H activation/hydroarylation has been developed for the first time, allowing for highly enantioselective synthesis of indoline derivatives via catalytic C-H activation. Commercially available Ru(II) arene complexes and chiral α-methylamines were employed as highly enantioselective catalysts. Based on a sterically rigidified chiral transient directing group, multisubstituted indolines were produced in up to 92% yield with 96% ee.

Persistent Placoid Maculopathy: Prognosis Factors and Functional Outcomes.

: To identify prognosis factors and functional outcomes of persistent placoid maculopathy (PPM). : We collected personal PPM cases and combined them with the data from the literature. : 68 eyes of 37 patients with PPM were analyzed, including six new cases.