Mechanistic insights into neosilyllithium-catalyzed hydroboration of nitriles, aldehydes, and esters: a DLPNO-CCSD(T) study.

Over the past few years, alkali and alkaline earth metals have emerged as alternative catalysts to transition metal organometallics to catalyze the hydroboration of unsaturated compounds. A highly selective and cost-effective lithium-catalyzed method for the synthesis of an organoborane has been established based on the addition of a B-H bond to an unsaturated bond (polarized or unpolarized) using pinacolborane (HBPin). In the present work, the neosilyllithium-catalyzed hydroboration of nitriles, aldehydes, and esters has been investigated using high-level DLPNO-CCSD(T) calculations to unravel the mechanistic pathways and substrate-dependent reactivity.

Tetranuclear {Ln} complexes possessing homometallic structural subunits: study of magnetic and photoluminescent properties.

A series of homometallic tetranuclear Ln complexes, [Ln(μ-OH){pyC(OH)O}(OCCMe)] [{pyC(OH)O} = monoanionic -diol form of di-2-pyridyl ketone; Ln = Nd (1), Eu (2), Tb (3), Dy (4), Er (5) and Yb (6)], have been synthesized and characterized. The asymmetric unit of each of the tetranuclear derivatives comprises the dinuclear motif, [Ln(μ-OH){pyC(OH)O}(OCCMe)]. The core structure of this Ln family possesses two homometallic structural subunits, LnIII3O, which are further connected through the bridging μ-OH ligands.

Nanostructuring of Dysprosocenium Single-Ion Magnets through Encapsulation in MOFs: A Promising Approach to Achieve High Axiality and Ambient Stability with Long-Range Ordering.

Implementing magnetic bistability in single-molecule magnets (SMMs) for quantum technologies requires precise nanostructuring, spatial organization, and environmental stabilization of magnetic centers. Here, we report the first encapsulation of the lanthanide-based SMM in three mesoporous diamagnetic MOFs─NU-1000, PCN-222-Zn, and MOF-177─to design hybrid magnetic structures with long-range ordering. An integrated approach combining DFT and AIMD simulations was carried out to unravel the structure, dynamics, stability, and nature of host-guest interactions in hybrid assemblies.

Peripheral Parking: A Bailout Strategy for Managing Dislodged Coronary Stents.

Coronary stent dislodgement is a rare but potentially life-threatening complication during percutaneous coronary intervention (PCI). It may occur due to complex anatomy, heavy calcification, tortuous vessels, or equipment malfunction, leading to embolization, vessel injury, or myocardial infarction if not promptly addressed. We present a case of stent dislodgement during transradial PCI, wherein a dislodged undeployed coronary stent migrated to the peripheral arterial system (left common iliac artery) seen on non-contrast computed tomography (NCCT).

Varying anion coordination in new families of dinuclear NiLn complexes: zero-field slow relaxation of magnetization and theoretical validations.

Herein, we report the room-temperature synthesis, structural characterization, and magnetic performances of two new families of dinuclear Ni-Ln complexes, [NiLn(HL)(NO)]·HO·CHCN (1a-1c) ( = 1 for Ln = Tb, and = 1.5 for Dy and Ho) and [NiLn(HL)(OAc)(HO)]Cl·5HO (2a-2c) (Ln = Tb, Dy, and Ho), developed utilizing the ligand HL (2-methoxy-6-[()-2'-hydroxymethyl-phenyliminomethyl]-phenol). Partial deprotonation of HL in the reaction medium provided HL, ideally suited for trapping Ni and selected 4f ions in its two adjacent pockets.

Interplay with Axial Halide Ligands (F, Cl, Br) to Modulate or Switch the Magnetic Anisotropy in Octahedral [Co(L)X] Complexes.

In this study, we intended to explore the role of axially coordinated halides (F, Cl, or Br) to modulate the magnetic anisotropy of Co(II) ion in octahedral [Co(L)X] {where X = Cl (1), Br (2), or F (3) and L = (E)-N-(2,6-dibenzhydryl-4-(trifluoromethoxy) phenyl)-1-(pyridin-2-yl)} complexes. The X-ray diffraction and structural elucidation revealed that 1 and 2 crystallized in tetragonal P4/n. The direct current (dc) magnetic susceptibility and magnetization data were collected and fitted or simulated to confirm the easy plane magnetic anisotropy for 1 and 2 with D = +28.

Electronic Structure, Covalency, and Magnetic Anisotropy in [AnCp3] (where An = Th-Cf) Complexes: Insights from First Principle Calculations.

Understanding the nature of actinide-ligand bonding, covalency, and magnetic properties is a burgeoning research topic in the field of actinide chemistry. In the present manuscript, we have thoroughly investigated the electronic structure, magnetic anisotropy of nine [AnCp] complexes (An = Th(III)-Cf(III)) using scalar relativistic density functional theory (SR-DFT) and complete active space self-consistent field (CASSCF) method to shed light on the nature of actinide-ligand covalency, with particular emphasis on the role of 5f versus 6d covalency in the bonding. DFT and CASSCF calculations predict 6d(Th), 5f6d (Pa), and 5f configurations for U-Cf analogues.

Concurrence of mining and climate change: environmental implications and mitigation strategies.

Mines degrade and contaminate environment at local or regional level posing risk to human health. However, the consequences of environmental degradation caused by mines on climate change is limited in literature. The review is carried out to understand the interplay of mines and climate change in perspective of its environmental implications.

Whispers of the Heart: Myocardial Infarction Induced by Beta Agonists.

Wellens syndrome is a relatively common yet fatal presentation of acute coronary syndrome and is considered a ST-segment elevation myocardial infarction (STEMI) equivalent. It often indicates an obstructive lesion in the proximal left anterior descending (LAD) artery and warrants early coronary angiography and revascularisation. We report the case of an elderly female in her 60s who presented to a primary health care centre with an acute-onset shortness of breath.

Chasing the High, Losing the Beat: A Case of Cocaine-Induced Myocardial Infarction.

Cocaine use is a well-established risk factor for various cardiovascular complications, including acute myocardial infarction (MI). The pathophysiological mechanisms responsible for cocaine-induced MI are multifactorial, encompassing coronary vasoconstriction, increased myocardial oxygen demand, and thrombosis. While cocaine-related cardiovascular events are more commonly seen in individuals with pre-existing risk factors, cases involving young, otherwise healthy individuals remain rare, yet they present a significant concern.

Retrieving a Peripherally Dislodged Coronary Stent: A Last Resort Approach.

A middle-aged man in his 50s with a history of percutaneous coronary intervention (PCI) in the left main coronary artery (LMCA) and right coronary artery presented with worsening exertional angina. Invasive coronary angiography revealed a significant diffuse lesion distal to the LMCA stent in the proximal left anterior descending (LAD) artery, prompting a decision to proceed with PCI. During the procedure, the stent detached from the balloon and became lodged at the proximal LMCA stent, resulting in hemodynamic collapse.

Hypocomplementemic Urticarial Vasculitis Syndrome: A Rare Form of Vasculitis.

Hypocomplementemic urticarial vasculitis syndrome (HUVS) is a rare autoimmune disorder characterized by recurrent urticarial lesions and acquired hypocomplementemia with systemic manifestations. Systemic involvement can either be present at the onset of disease or develop later. Here, we present a rare case of a 22-year-old female, who initially presented with generalized rash and was eventually diagnosed with HUVS.

Single-ion magnet behaviour in highly axial lanthanide mononitrides encapsulated in boron nitride nanotubes: a quantum chemical investigation.

Lanthanide-based single-ion magnets (Ln-SIMs) have garnered significant interest for their potential application in molecular-level information storage devices. Among various strategies to enhance the magnetization blocking barrier in SIMs, synthesizing highly axially symmetric compounds is the most promising approach. In the present work, using state-of-the-art computational tools, we have thoroughly examined the electronic structure, bonding, and magnetic anisotropy of lanthanide mononitrides (where Ln = Dy(III) and Tb(III)) and their encapsulation in zigzag boron nitride nanotubes (BNNTs) with diameters of (8,0) and (9,0) to explore novel hybrid assemblies.

Intramolecular Redox-Driven Synthesis of Mono- and Diradical Iridium(III) Complexes: Insights into Molecular and Electronic Structure, Electrochemistry, and Spin-Communication.

Two π-radical complexes containing bisazo-aromatic-centered radical anion (1) were synthesized through in-situ electron transfer from metal-to-ligand using [Ir] and 2-(2-Pyridylazo)azobenzene (1) in inert hydrocarbon solvent. These are characterized as diradical [Ir(1)] [2] and monoradical [Ir(1)Cl(PPh)] 3. In contrast, a rare metal-mediated hydrolytic cleavage of the C(sp)-N bond occurred in protic solvent resulting in quaternary radical complex [Ir(1)(1')(PPh)] (4).

Electrochemically grafted molecular layers as on-chip energy storage molecular junctions.

Molecular junctions (MJs) are celebrated nanoelectronic devices for mimicking conventional electronic functions, including rectifiers, sensors, wires, switches, transistors, negative differential resistance, and memory, following an understanding of charge transport mechanisms. However, capacitive nanoscale molecular junctions are rarely seen. The present work describes electrochemically (E-Chem) grown covalently attached molecular thin films of 10, 14.

Conversion of aromatic methyl ketones to esters and carboxylic acids using -phthalaldehyde as an oxidant.

Herein we describe a two-step conversion of aromatic methyl ketones to esters and carboxylic acids employing -phthalaldehyde as an oxidant. In the first step, -phthalaldehyde oxidizes the methyl group to 1-indanone, which acts as a leaving group in a subsequent regioselective retro-Claisen condensation to form esters and carboxylic acids. The mild oxidation conditions ensure the method is applicable to a broad range of substrates.

Unravelling the electronic structure, bonding, and magnetic properties of inorganic dysprosocene analogues [Dy(E)] (E = N, P, As, CH).

Organometallic sandwich complexes of Dy(III) ion are ubiquitous for designing high-temperature single-ion magnets with blocking temperatures close to the liquid nitrogen boiling point. Magnetic bistability at the molecular level makes them potential candidates for nano-scale information storage materials. In the present contribution, we have thoroughly investigated the electronic structure, bonding, covalency, and magnetic anisotropy of inorganic dysprosocene complexes with a general formula of [Dy(E)] (where E = N, P, As, CH) using state-of-the-art scalar relativistic density functional theory (SR-DFT), and a multiconfigurational complete active space self-consistent field (CASSCF) method with the N-electron valence perturbation theory (NEVPT2).

Palladium catalysed cross coupling reactions on 2,3-isoxazol-17α-ethynyltestosterone, their anti-cancer activity, molecular docking studies and ADMET analysis.

In the current study, the Sonogashira coupling reaction of danazol with aryl halides was carried out, yielding new aryl substituted danazol derivatives. The synthetic compounds were examined for anti-cancer potential on the HeLa human cervical cancer cell line, and they showed promising cytotoxic action. Synthesized compounds 2, 4 and 5 inhibited the growth of HeLa cervical cancer cells, potentially making them effective anti-cancer drugs in the future.

Substituted fullerenes as a promising capping ligand towards stabilization of exohedral Dy(III) based single-ion magnets: a theoretical study.

Organometallic dysprosocenium-based molecular magnets are the forefront runners in offering giant magnetic anisotropy and blocking temperatures close to the boiling point of liquid nitrogen. Attaining linearity in the organometallic dysprosocenium complexes is the key to generating giant magnetic anisotropy and blocking barriers. In the present study, we have unravelled the coordination ability of the substituted fullerene (CX) (where X = CCH, B, and N) generated by fencing around the five-membered ring of fullerene towards stabilizing a new family of exohedral dysprosium organometallic complexes showcasing giant magnetic anisotropy and blockade barriers.

hydrolysis of a carbophosphazene ligand leads to one-dimensional lanthanide coordination polymers. Synthesis, structure and dynamic magnetic studies.

An hydrolysis of the P-Cl bonds of the carbophosphazene [{NC(NMe)}{NPCl}] (L) in the presence of hydrated lanthanide(III) nitrates in a dichloromethane and methanol (2 : 1) solvent mixture afforded a series of novel 1D coordination polymers: [{Ln(L)(NO)(CHOH)(HO)} (Cl)] {where Ln(III) = Gd (1), Tb (2), Dy (3), or Er (4) and L is the hydrolyzed carbophosphazene (L) ligand}. X-ray crystallographic analysis revealed that complexes 1-4 are isostructural and crystallized in the monoclinic crystal system having 2/ space group. The coordination polymers are formed because of the involvement of the geminal P(O)(OH) moieties of the carbophosphazene ligand.

Metal-free platforms for molecular thin films as high-performance supercapacitors.

Controlling chemical functionalization and achieving stable electrode-molecule interfaces for high-performance electrochemical energy storage applications remain challenging tasks. Herein, we present a simple, controllable, scalable, and versatile electrochemical modification approach of graphite rods (GRs) extracted from low-cost Eveready cells that were covalently modified with anthracene oligomers. The anthracene oligomers with a total layer thickness of ∼24 nm on the GR electrode yield a remarkable specific capacitance of ∼670 F g with good galvanostatic charge-discharge cycling stability (10 000) recorded in 1 M HSO electrolyte.

Eight-coordinate mono- and dinuclear Dy(III) complexes containing a rigid equatorial plane and an anisobidentate carboxylate ligand in the axial position: synthesis, structure and magnetism.

A rigid pentadentate chelating ligand (HL) has been utilized to synthesize a series of octacoordinate mononuclear complexes, [Dy(L)(PhPO)(OOCR)] (where R = CH (1), C(CH) (2), CF (3)) and a dinuclear complex, [Dy(L)(PhPO){(OOC)CH}] (4) based on the highly anisotropic Dy(III) ion. All the complexes were structurally characterized by single-crystal X-ray diffraction studies. The complexes were formed by the coordination action of the dianionic pentadentate ligand [L], one phosphine oxide, and carboxylate ligands.

A highly anisotropic family of hexagonal bipyramidal Dy(III) unsaturated 18-crown-6 complexes exceeding the blockade barrier over 2700 K: a computational exploration.

In the present work, we have explored a series of unsaturated hexa-18-crown-6 (U18C6) ligands towards designing highly anisotropic Dy(III) based single-ion magnets (SIMs) with the general formula [Dy(U18C6)X] (where U18C6 = [CHO] (1), [CHS] (2), [CHSe] (3), [CHOS] (4), [CHOSe] (5) and X = F, Cl, Br, I, OBu and OSiPh). By analysing the electronic structure, bonding and magnetic properties, we find that the U18C6 ligands prefer stabilising the highly symmetric eight-coordinated hexagonal bipyramidal geometry (HBPY-8), which is the source of the near-Ising type anisotropy in all the [Dy(U18C6)X] complexes. Moreover, the ability of sulfur/selenium substituted U18C6 ligands to stabilize the highly anisotropic HBPY-8 geometry makes them more promising towards engineering the equatorial ligand field compared to substituted saturated 18C6 ligands where the exodentate arrangement of the S lone pairs results in low symmetry.

Support Vector Machine-Based Prediction Models for Drug Repurposing and Designing Novel Drugs for Colorectal Cancer.

Colorectal cancer (CRC) has witnessed a concerning increase in incidence and poses a significant therapeutic challenge due to its poor prognosis. There is a pressing demand to identify novel drug therapies to combat CRC. In this study, we addressed this need by utilizing the pharmacological profiles of anticancer drugs from the Genomics of Drug Sensitivity in Cancer (GDSC) database and developed QSAR models using the Support Vector Machine (SVM) algorithm for prediction of alternative and promiscuous anticancer compounds for CRC treatment.

Effect of diamagnetic Zn(II) ions on the SMM properties of a series of trinuclear ZnDy and tetranuclear ZnDy (Ln = Dy, Tb, Gd) complexes: combined experimental and theoretical studies.

To study the effect of diamagnetic ions on magnetic interactions, utilizing a compartmental ligand ()-2-(hydroxymethyl)-4-methyl-6-((quinolin-8-ylimino)methyl)phenol (LH), two different series of Zn-Ln complexes, namely the trinuclear series of [DyZn(L)(μ-OAc)(CHOH)]·NO·MeOH (1), [TbZn(L)(μ-OAc)(CHOH)]·NO·5MeOH·HO (2), and [GdZn(L)(μ-OAc)(CHOH)]·NO·MeOH·CHCl (3) and the tetranuclear series of [DyZn(LH)(NO)(μOAc)]·NO·MeOH·HO (4), [TbZn(LH)(NO)(μ-OAc)]·NO·MeOH·2HO (5), and [GdZn(LH)(NO)(μ-OAc)]·NO·MeOH·2HO (6), were synthesized. Trinuclear Zn-Ln complexes 1-3 consist of one Ln ion sandwiched between two peripheral Zn ions forming a bent type Zn-Dy-Zn array with an angle of 110.64°.