Advances in lanthanide cyclononatetraenyl chemistry.

Cyclononatetraenyl (Cnt) is a nine-membered monoanionic aromatic ligand. Despite its early discovery in 1963, it has been rarely utilised in coordination chemistry, which is mainly due to its large diameter and easy skeletal rearrangement. Only in 2017, the first lanthanide Cnt complex was synthesised, marking the beginning of a new era in organolanthanide chemistry.

Experimental Spin State Determination of Iron(II) Complexes by Hirshfeld Atom Refinement.

In this study, we present the first experimental determination of the spin state of transition metal complexes by using Hirshfeld Atom Refinement. For the demonstration, the two iron(II) complexes, (NH4)2Fe(SO4)2*6H2O and [Fe(pic)3]Cl2*EtOH were investigated. The method involves the refinement using wavefunctions of different spin multiplicity and comparison against experimental diffraction data by means of refinement indicators and residual electron density.

Dinuclear Rare-Earth β-Diketiminates with Bridging 3,5-Di-butyl-catecholates: Synthesis, Structure, and Single-Molecule Magnet Properties.

The dinuclear β-diketiminato complex [LClDy(μ-Cl)DyL(THF)] () (L = {2,6-PrCH-NC(Me)CHC(Me)N-2,6-PrCH}) was obtained by reaction of DyCl with KL in a molar ratio of 1:1 and used for the preparation of the mixed-ligand complex [LDy(μ-3,5-Cat)] () by salt metathesis reaction with 3,5-CatK (3,5-Cat -3,5-di--butyl-catecholate). Reactions of 3,5-CatNa with [LLnCl(THF)] (Ln = Dy, Y) ligated with the less bulky ligand L = {2,4,6-MeCH-NC(Me)CHC(Me)N-2,4,6-MeCH} afforded the mixed-ligand THF-containing complexes [LLn(μ-3,5-Cat)(THF)] (Ln = Dy (), Y ()). All new complexes were fully characterized, and the solid-state structures were determined by single-crystal X-ray diffraction.

Extended chains in vanadium O-centered complex [VOSeI]: synthesis and structure.

O-centered tetranuclear vanadium selenoiodide [VOSeI] (1) was synthesized by an ampoule method from the elements with addition of water. Its X-ray crystal structure (space group 2/, = 21.146(2) Å, = 5.

Solution equilibrium and redox properties of metal complexes with 2-formylpyridine guanylhydrazone derivatives: Effect of morpholine and piperazine substitutions.

Schiff bases derived from aminoguanidine are extensively investigated for their structural versatility. The tridentate 2-formylpyridine guanylhydrazones act as analogues of 2-formyl or 2-acetylpyridine thiosemicarbazones, where the thioamide unit is replaced by the guanidyl group. Six derivatives of 2-formylpyridine guanylhydrazone were synthesized and their proton dissociation and complex formation processes with Cu(II), Fe(II) and Fe(III) ions were studied using pH-potentiometry, UV-visible, NMR and electron paramagnetic resonance spectroscopic methods.

A Comparative Pharmacokinetics Study of Orally and Intranasally Administered 8-Nitro-1,3-benzothiazin-4-one (BTZ043) Amorphous Drug Nanoparticles.

BTZ043 is an 8-nitro-1,3-benzothiazin-4-one with potency against multidrug-resistant . Low solubility and hepatic metabolism are linked to poor oral bioavailability. Amorphous drug nanoparticles (ADN) were formulated to improve the bioavailability.

Insights into the Electrochemical Oxidation and Reduction of Nickel Oxide Surfaces.

Surface oxidation/reduction processes, driven by varying electrochemical potentials, can substantially impact catalyst effectiveness and, consequently, electrolyzer performance. This study combines theoretical and experimental approaches to explore the surface redox behavior of nickel oxides, which are cost-effective and efficient catalysts for many electrochemical reactions. Surface Pourbaix diagrams for three different phases of nickel oxides, i.

A Novel Polymer Film to Develop Heart Valve Prostheses.

Polymer heart valves are a promising alternative to bioprostheses, the use of which is limited by the risks of calcific deterioration of devitalized preserved animal tissues. This is especially relevant in connection with the increasingly widespread use of transcatheter valves. Advances in modern organic chemistry provide a wide range of polymers that can replace biological material in the production of valve prostheses.

Silver CVD and ALD Precursors: Synthesis, Properties, and Application in Deposition Processes.

This review summarized the developments in the field of volatile silver complexes, which can serve as precursors in gas-transport reactions for the production of thin films and metal nanoparticles via chemical vapor deposition (CVD) and atomic layer deposition (ALD). Silver-based films and nanoparticles are widely used in various high-tech fields, including medicine. For effective use in CVD and ALD processes, the properties of silver precursors must be balanced in terms of volatility, thermal stability, and reactivity.

MnCl(CNH): Insights into a Luminescent Transition Metal-Melem Complex.

In this work, the (MnCl(CNH) complex has been synthesized via solid-state reaction between manganese (II) chloride and melamine in the molar ratio of 1:2. A similar synthesis has been repeated with CoCl, and FeCl, resulting in two new metal-melam complexes (FeCl(CNH) and CoCl(CNH)). MnCl(CNH) crystallizes in the monoclinic crystal system with the space group 2/.

Re-design and evaluation of diclofenac-based carborane-substituted prodrugs and their anti-cancer potential.

In this study, we investigated a novel anti-cancer drug design approach by revisiting diclofenac-based carborane-substituted prodrugs. The redesigned compounds combine the robust carborane scaffold with the oxindole framework, resulting in four carborane-derivatized oxindoles and a unique zwitterionic amidine featuring a nido-cluster. We tested the anti-cancer potential of these prodrugs against murine colon adenocarcinoma (MC38), human colorectal carcinoma (HCT116), and human colorectal adenocarcinoma (HT29).

Tin-Chelated Trisphosphineoxide Scorpionate Rare-Earth Porphyrinate Complexes: Synthesis and Photophysical Properties.

A series of seven-coordinated monoporphyrinate rare-earth(III) complexes featuring a novel tripodal tin-chelated trisphosphineoxide scorpionate ligand with the general formula [(TPP)Ln(PPhO)Sn] (Ln = Y, La, Dy, Er, Ho, Yb; TPP = 5,10,15,20-tetraphenylporphyrinate) were synthesized by reactions of the potassium tripodal scorpionate ligand [Sn(PPhO)K] with porphyrinate rare-earth metal chlorides [(TPP)LnCl(dme)] (Ln = Y, Dy, Er, Ho, Yb) or porphyrinate lanthanum borohydride [(TPP)LaBH(thf)]. The complexes were characterized by single-crystal X-ray diffraction, NMR spectroscopy, and ion mobility mass spectrometry. All complexes emit weak red TPP-based fluorescence, accompanied by near-infrared emission of Er, Ho (rather weak), and Yb (relatively intense with a quantum yield of 1% in dichloromethane solution) of the corresponding complexes.

ALD and CVD deposition of pure thin gold films from a stable dimethylgold(III) precursor.

The synthesis and thermal properties of a volatile dimethylgold(III) complex MeAuSSP(OPr) are reported. Unlike most other volatile Au(I) and Au(III) compounds, the complex is stable upon storage, does not require any special handling conditions, and exhibits both good volatility and thermal stability. The compound was tested as a CVD and ALD precursor, yielding good quality films in both processes.

Toward Rhenium-based Circularly Polarized OLEDs Using Tailored Chiral Re(CO)3 Emitters.

Chiral rhenium(I) emitters showing 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 firstly  demonstrated CPEL from rhenium emitters.

Luminescence and Generation of Reactive Oxygen Species in Solution by Ta6Br12 Clusters.

An intrinsic metal cluster NIR-II emission of the {Ta6Br12}2+ aqua/hydroxocomplexes was determined in aqueous solutions under inert atmosphere. The photoluminescence (PL) is enhanced in D2O, and the lifetime scale expands from nanoseconds to microseconds. Possible cluster emission transitions have been assigned and analyzed from a computational perspective.

Synthesis and reactivity of a six-membered heterocyclic 1,3-diphosphaallene.

1,3-Diphosphaallenes are a new class of heavier heteroallenes and show a fascinating chemical behavior and reactivity. Herein we report on the room temperature transformation of gallaphosphene LGa(OCP)PGaL 1 (L = HC[C(Me)N(Ar)], Ar = 2,6-i-PrCH) to the six-membered metallaheterocycle LGa(PCP)OGaL 2 featuring a LGa-substituted 1,3-diphosphaallene unit. The possible mechanism of formation of 2 is supported by quantum chemical calculations, which revealed that the formation of 2 is energetically more favorable ( 2 kcal mol) than the formation of 1 at ambient temperature.

Specific gFET-Based Aptasensors for Monitoring of Microbiome Quality: Quantification of the Enteric Health-Relevant Bacterium Roseburia Intestinalis.

Roseburia intestinalis, enriched in the gut, is closely associated with obesity, intestinal inflammation, and other diseases. A novel detection method for R. intestinalis to replace the commonly used 16S rRNA sequencing technique is aim to developed, thus enabling real-time and low-cost monitoring of gut microbiota.

Reversible formation of tetraphenylpentalene, a room temperature stable antiaromatic hydrocarbon.

1,3,4,6-Tetraphenylpentalene (PhPn) has been synthesised by chemical oxidation of the corresponding pentalenide complex Mg[PhPn] with iodine. PhPn is a rare example of a room-temperature stable hydrocarbon that is antiaromatic by Hückel's rule and has been fully characterised by NMR and UV-vis spectroscopy, mass spectrometry as well as single-crystal X-ray diffraction. Quantum chemical studies including nucleus-independent chemical shift (NICS) and anisotropy of the induced current density (ACID) calculations showed the existence of an 8π antiaromatic core decorated with four independent 6π aromatic substituents.

Near-Infrared Light-Induced Spin-State Switching Based on Fe(II)-Hg(II) Spin-Crossover Network.

The development of molecular switches with tunable properties has garnered considerable interest over several decades. A novel spin-crossover (SCO) material based on iron(II) complexes incorporating 4-acetylpyridine (4-acpy) and [Hg(SCN)] anions was synthesized and formulated as [Fe(4-acpy)][Hg(μ-SCN)] (1). Compound 1 is crystallized in a three-dimensional network in the non-centrosymmetric orthorhombic space group Pna2 with two octahedral [Fe(4-acpy)(NCS)] entities featuring two distinct Fe centers (Fe1 and Fe2).

Highly Porous Scandium(III) Tetrafluoroisophthalate Framework for Adsorptive Separation of Light Alkanes.

The separation of light alkanes is one of the most important tasks for modern industry due to the widespread use of ethane and propane as chemical feedstocks. Their extraction from natural gas is a challenging task and is now carried out by cryogenic distillation at a limited number of plants around the world. The development of new materials for adsorption separation is therefore important.

A Stable Carbon-Centered Radical Showing Six Amphoteric Redox States.

An air- and moisture-stable hydrocarbon radical with four six- and three five-membered rings alternately fused to a heptacycle was obtained by ortho fusion in a suitably ortho,ortho'-substituted diphenylfluorene and subsequent re-establishment of the conjugation. The radical was obtained in five consecutive steps from commercially available starting materials with a total yield of 34 %; key steps are Suzuki couplings and cyclizing SAr reactions. Mesityl substituents at the five-membered rings ensure the stability of the radical.

Gradual Acidification at the Oral Biofilm-Implant Material Interface.

The colonization of dental implants by oral biofilms causes inflammatory reactions that can ultimately lead to implant loss. Therefore, safety-integrated implant surfaces are under development that aim to detect bacterial attachment at an early stage and subsequently release antibacterial compounds to prevent their accumulation. Since primary oral colonizers ferment carbohydrates leading to local acidification, pH is considered a promising trigger for these surfaces.