Structure and Magnetic Properties of the = 3 Ruddlesden-Popper Oxyfluoride LaSrFeOF.

Ruddlesden-Popper (RP) compounds of the general formula (AX)(ABX) with their unique sequence of perovskite-like (ABX) and rock-salt-like units (AX) promise applications in diverse fields such as catalysis and superconductivity. Fluorination of RP oxides often leads to dramatic changes in the material properties, caused by differences in the atomic and electronic structure. While current research focuses on fluorination of = 1 type RP oxides (ABO), = 3 RP oxyfluorides have remained elusive.

Cooperative spin crossover leading to bistable and multi-inert system states in an iron(III) complex.

Cooperativity among spin centres has long been the royal road in spin crossover (SCO) research to impose magnetic bistability in terms of thermal hysteresis. In this work we access magnetic multi-inert states of the iron(III) compound {FeL[B(Ph)]} ≡ FeB at low temperature, in addition to thermal bistability. The packing of the low-spin and high-spin forms of crystalline FeB differs only marginally what ultimately leads to structural conservatism.

Binucleating Jäger-type {(NO)} ligands: magnetic and electronic interactions of Fe(II), Ni(II) and Cu(II) across an in-plane TTF-bridge.

The simultaneous presence of different electrophores provides an interesting playground for responsive materials. Herein, we present the incorporation of a twice-reversibly oxidizable tetrathiafulvalene (TTF) unit into a binucleating ligand, bridging two metal centers in a fully conjugated plane. A two-step synthesis scheme gave the D symmetric Schiff base-like ligand HL in moderate yields from which the corresponding copper(II) [Cu2L], nickel(II) [Ni2L], [Ni2L(py)4] and iron(II) complexes [Fe2L(py)4], [Fe2L(dmap)4] and [Fe2L(bpee)2]·1 Tol could be obtained.

Exploring the Magnetic Interactions in Two Novel Cyanide-Bridged Homo- and Heterometallic Hexadecanuclear Complexes.

Two novel isostructural cyanide-bridged hexadecanuclear complexes with the general formula {[Fe(CN)][M{en(Bn)py}]} [M=Fe (1), Ni (2)] have been synthesized. The structural analyses disclose the presence of multivalent Fe centres with different spin states in complex 1 whereas all the Fe centres share a conserved oxidation state in complex 2. The DC magnetic study revealed antiferromagnetic interactions between the adjacent metal centres and ferrimagnetic behaviour in 1.

Isostructural Series of Ni(II), Pd(II), Pt(II), and Au(III) Azido Complexes with a N^C^N Pincer Ligand to Elucidate Trends in the iClick Reaction Kinetics and Structural Parameters of the Triazolato Products.

An isoelectronic and isostructural series of cyclometalated azido complexes [M(N)(dpb)] with M = Ni(II), Pd(II), Pt(II), and Au(III) based on the N^C^N pincer ligand 1,3-di(2-pyridyl)phenide (dpb) was characterized by X-ray diffraction analysis and investigated for reactivity in the iClick reaction with a wide range of internal and terminal alkynes by using H and F NMR spectroscopy. Reaction rate constants were found to increase with greater charge density in the order Ni(II) > Pd(II) > Pt(II) > Au(III). Terminal alkynes R-C≡C-R' with strongly electron-withdrawing groups R and R' exhibited faster kinetics than those with electron-donating substituents in the order CF > ketone > ester > H > phenyl ≫ amide, while R = CH resulted in complete loss of reactivity.

New 4,5-Diarylimidazol-2-ylidene-iodidogold(I) Complexes with High Activity against Esophageal Adenocarcinoma Cells.

Inspired by the vascular-disrupting agent combretastatin A-4 and recently published anticancer active -heterocyclic carbene (NHC) complexes of Au(I), a series of new iodidogold(I)-NHC complexes was synthesized and characterized. The iodidogold(I) complexes were synthesized by a route involving van Leusen imidazole formation and -alkylation, followed by complexation with AgO, transmetalation with chloro(dimethylsulfide)gold(I) [Au(DMS)Cl], and anion exchange with KI. The target complexes were characterized by IR spectroscopy, H and C NMR spectroscopy, and mass spectrometry.

The Acceptability of a Recovery Group Intervention in Acute Inpatient Mental Health Wards.

The aim of the present study was to evaluate the feasibility and explore the service user experience of a recovery-focused group intervention delivered in acute inpatient wards in a National Health Service (NHS) Trust in England, United Kingdom. Feedback from the Recovery Group Questionnaire given to patients who had attended the Recovery Group whilst admitted to acute inpatient wards was collated and analysed. The results suggest that patients found the group useful and supportive, as well as easy to follow.

Rare, common, alien and native species follow different rules in an understory plant community.

Biological invasions are a leading threat to biodiversity globally. Increasingly, ecosystems experience multiple introductions, which can have significant effects on patterns of diversity. The way these communities assemble will depend partly on whether rare and common alien species respond to environmental predictors in the same manner as rare and common native species, but this is not well understood.

Self-Assembled Fluorescent Block Copolymer Micelles with Responsive Emission.

Responsive fluorescent materials offer a high potential for sensing and (bio-)imaging applications. To investigate new concepts for such materials and to broaden their applicability, the previously reported non-fluorescent zinc(II) complex [Zn(L)] that shows coordination-induced turn-on emission was encapsulated into a family of non-fluorescent polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) diblock copolymer micelles leading to brightly emissive materials. Coordination-induced turn-on emission upon incorporation and ligation of the [Zn(L)] in the P4VP core outperform parent [Zn(L)] in pyridine solution with respect to lifetimes, quantum yields, and temperature resistance.

Photocatalytic Degradation of 4,4'-Isopropylidenebis(2,6-dibromophenol) on Sulfur-Doped Nano TiO.

In present work, we examine the photocatalytic properties of S-doped TiO (S1, S2) compared to bare TiO (S0) in present work. The photocatalytic tests were performed in alkaline aqueous solutions (pH = 10) of three differently substituted phenols (phenol (I), 4,4'-isopropylidenebisphenol (II), and 4,4'-isopropylidenebis(2,6-dibromophenol) (III)). The activity of the catalysts was evaluated by monitoring I, II, III degradation in the reaction mixture.

Quenched Lewis Acidity: Studies on the Medium Dependent Fluorescence of Zinc(II) Complexes.

Three new zinc(II) coordination units [Zn(1-3)] based on planar-directing tetradentate Schiff base-like ligands H (1-3) were synthesized. Their solid-state structures were investigated by single crystal X-ray diffraction, showing the tendency to overcome the square-planar coordination sphere by axial ligation. Affinity in solution towards axial ligation has been tested by extended spectroscopic studies, both in the absorption and emission mode.

The Fibronectin-ILT3 Interaction Functions as a Stromal Checkpoint that Suppresses Myeloid Cells.

Suppressive myeloid cells inhibit antitumor immunity by preventing T-cell responses. Immunoglobulin-like transcript 3 (ILT3; also known as LILRB4) is highly expressed on tumor-associated myeloid cells and promotes their suppressive phenotype. However, the ligand that engages ILT3 within the tumor microenvironment and renders tumor-associated myeloid cells suppressive is unknown.

Integrating Physicians Into Lean Quality Improvement Through a Structured Educational Program: The ECLIPSE Program.

In the increasingly complex health care system, physicians require skills and knowledge to participate with multidisciplinary team members in quality improvement (QI) that adds value to health care organizations. The Educational and Clinical Leaders Improving Performance with Structured E3L training (ECLIPSE) program was developed to address this challenge. Clinically relevant components of lean management were leveraged to create an online, flipped-classroom curriculum, and this was paired with Kaizen adapted specifically for physicians and multidisciplinary clinicians to promote experiential skills utilization.

Ni, Pd, and Pt complexes of a tetradentate dianionic thiosemicarbazone-based O^N^N^S ligand.

New tetradentate phenolate O^N^N^S thiosemicarbazone (TSC) ligands and their Ni(ii), Pd(ii) and Pt(ii) complexes were studied. The diamagnetic and square planar configured orange or red complexes show reversible reductive electrochemistry and in part reversible oxidative electrochemistry at very moderate potentials. DFT calculations show essentially pyridyl-imine centred lowest unoccupied molecular orbitals (LUMO) while the highest occupied molecular orbitals (HOMO) receive contributions from the phenolate moiety, the metal d orbitals and the TSC thiolate atom in keeping with UV-vis spectroelectrochemistry.

A Fluorescence-Detected Coordination-Induced Spin State Switch.

The response of the spin state to variation of the coordination number (CISSS) is a promising and viable approach to smart sensor materials, yet it suffers to date from insensitive detection. Herein, we present the synthetic access to a family of planar nickel(II) complexes, whose CISSS is sensitively followed by means of fluorescence detection. For this purpose, nickel(II) complexes with four phenazine-based Schiff base-like ligands were synthesized and characterized through solution-phase spectroscopy (NMR and UV-vis), solid-state structure analysis (single-crystal XRD), and extended theoretical modeling.

Long-Term Colloidally Stable Aqueous Dispersions of ≤5 nm Spinel Ferrite Nanoparticles.

Applications in biomedicine and ferrofluids, for instance, require long-term colloidally stable, concentrated aqueous dispersions of magnetic, biocompatible nanoparticles. Iron oxide and related spinel ferrite nanoparticles stabilized with organic molecules allow fine-tuning of magnetic properties via cation substitution and water-dispersibility. Here, we synthesize≤5 nm iron oxide and spinel ferrite nanoparticles, capped with citrate, betaine and phosphocholine, in a one-pot strategy.

Declining Chlamydia and Gonorrhea Diagnoses Among Pregnant Women in South Carolina, 2008 to 2018.

Background: Reported US cases of chlamydia and gonorrhea have increased since 2000, whereas studies in select populations suggest that the prevalence of these diseases has decreased. We sought to determine if these diagnoses are increasing among pregnant women delivering at our center.

Methods: This is a retrospective study of women delivering at least 1 infant >18 weeks of gestation at the Medical University of South Carolina for 11 years (2008-2018).

Synthesis of Zn-based 1D and 2D coordination polymer nanoparticles in block copolymer micelles.

Nanoparticles of the 1D and 2D coordination polymers [Zn(OAc)(bipy)] and [Zn(TFA)(bppa)] were prepared, employing polystyrene--poly(4-vinylpyridine) diblock copolymers with different weight fractions of the 4-vinylpyridine (4VP) block and comparable overall molecular weights of ≈ 155 kg mol as template (SV-15 and SV-42 with 15 and 42 wt% 4VP, respectively). [Zn(OAc)(bipy)] nanoparticles were successfully synthesised within the 4VP core of SV-42 micelles, showing a core size of = 47 ± 5 nm and a hydrodynamic diameter of = 157 ± 46 nm, determined by transmission electron microscopy (TEM) and dynamic light scattering (DLS). The crystallinity of the composite is quite low, showing only low intensity reflexes in the powder X-ray diffraction (PXRD) pattern with the highest particle load.

Spin crossover modulation in a coordination polymer with the redox-active bis-pyridyltetrathiafulvalene (pyTTF) ligand.

A one-dimensional Fe coordination polymer (CP) has been formed which includes the redox-active ligand bis-pyridyltetrathiafulvalene (pyTTF) and a Schiff base-like NO ligand. This CP is both spin crossover (SCO) and redox-active in the solid-state, and chemical oxidation results in SCO modification.

A four-parameter system for rationalising the electronic properties of transition metal-radical ligand complexes.

A system of four principal parameters is reported that provides a unified description of the electronic and chemical properties of radical-ligand coordination compounds. This type of parametrisation applies to compositionally different types of radical-ligands, and the principal parameters rank in the following order: (a) coordination mode (metal-ligand orbital alignment) > (b) metal linkage > (c) ligand charge > (d) geometric strain (on orbital overlap). A series of group-10 metal complexes of an open-shell thiolate-arene-thiolate ligand suits to differentiate between three of the four effects in a clear-cut fashion, which allowed sorting these into a semi-quantitative order for the first time.

Phosphorus Analogues of [Ni(bpy)]: Synthesis and Application in Carbon-Halogen Bond Activation.

The neutral, homoleptic pyridylphosphininenickel(0) complex [Ni(2-Py-4,6-Ph-PCH)] () has been obtained by reaction of the formal Ni(0) source [(IPr)Ni(HC═CHSiMe)] with 2 equiv of 2-(2'-pyridyl)-4,6-diphenylphosphinine (). Compound can be oxidized both electrochemically and through the use of ferrocenium salts, to afford the corresponding Ni(I) complexes []BF, [(THF)]PF, and [](BAr). The structures of these salts reveal an interesting dependence on the nature of the anion.

Water-Triggered Photoinduced Electron Transfer in Acetonitrile-Water Binary Solvent. Solvent Microstructure-Tuned Reactivity of Hydrophobic Solutes.

The solvent-composition dependence of quenching triplet states of benzophenone (BP) by anisole in acetonitrile-water (ACN-HO) mixtures was investigated by laser flash photolysis over the water mole fraction () increasing from 0 to 0.92. Single exponential decay of BP was observed over the whole composition range.

Iron(II) Spin Crossover Complexes Based on a Redox Active Equatorial Schiff-Base-Like Ligand.

In this work, two iron(II) coordination compounds with a NO coordinating Schiff base-like ligand bearing a redox active tetrathiafulvalene (TTF) unit and pyridine or -1,2-bis(4-pyridylethylene) as an axial ligand are synthesized. Crystals suitable for single X-ray structure analysis were obtained for the new ligand. The complexes were characterized by magnetic susceptibility measurements, -dependent UV-vis spectroscopy, and cyclic voltammetry.

Selective metalation of phenol-type proligands for preparative organometallic chemistry.

The selective C-metalation of phenol ester derived proligands is a readily applicable addition to state-of-the-art protocols toward cyclometalated structures, in particular of the base metals. The approach is demonstrated by the ortho-nickelation of a 1,10-phenanthroline based strong-field ligand platform that is a sought-after motif in the field of base-metal photochemistry.