(η-Cyclooctatetraene)(η-fluorenyl)titanium: a processable molecular spin qubit with optimized control of the molecule-substrate interface.

Depositing single paramagnetic molecules on surfaces for sensing and quantum computing applications requires subtle topological control. To overcome issues that are often encountered with sandwich metal complexes, we exploit here the low symmetry architecture and suitable vaporability of mixed-sandwich [FluTi(cot)], Flu = fluorenyl, cot = cyclooctatetraene, to drive submonolayer coverage and select an adsorption configuration that preserves the spin of molecules deposited on Au(111). Electron paramagnetic resonance spectroscopy and quantum computation evidence a d ground state that protects the spin from phonon-induced relaxation.

Crystal structure of a three-coordinate lithium complex with monodentate phenyl-oxazoline and hexa-methyl-disilyl-amide ligands.

The reaction of lithium hexa-methyl-disilyl-amide, [Li{N(Si(CH))}] (LiHMDS), with 4,4-dimethyl-2-phenyl-2-oxazoline (Phox, CHNO) in hexane produced colourless crystals of bis-(4,4-dimethyl-2-phenyl-2-oxazoline-κ)(hexa-methyl-disilyl-amido-κ)lithium, [Li(CHNSi)(CHNO)] or [Li{N(Si(CH))}(Phox)] in high yield (89%). Despite the 1:1 proportion of the starting materials in the reaction mixture, the product formed with a 1:2 amide:oxazoline ratio. In the unit cell of the 2/ space group, the neutral mol-ecules lie on twofold rotation axes coinciding with the Li-N(amide) bonds.

A new approach to study semi-coordination using two 2-methyl-5-nitroimidazole copper(ii) complexes of biological interest as a model system.

Two novel copper(ii) complexes [Cu(2mni)(HO)](NO)·2HO (1) and [Cu(2mni)(NO)] (2), where 2mni is 2-methyl-5-nitroimidazole, were prepared and characterized in the solid state using single-crystal and powder X-ray diffraction analyses, EPR, electronic and vibrational spectroscopies (FTIR and Raman), and thermogravimetric methods. Both products present an elongated distorted octahedral geometry with axial Cu-O bond lengths of 2.606(14) and 2.

Palladium-Catalyzed Direct Selanylation of Chalcogenophenes and Arenes Assisted by 2-(Methylthio)amide.

The direct and selective conversion of a C-H bond into a C-Se bond remains a significant challenge, which is even more intricate with substrates having an innate regioselectivity under several reaction conditions, such as chalcogenophenes. We overrode their selectivity toward selanylation using palladium, copper, and the 2-(methylthio)amide directing group. This chelation-assisted direct selanylation was also suitable for mono and double ortho functionalization of arenes.

A dysprosium single molecule magnet outperforming current pseudocontact shift agents.

A common criterion for designing performant single molecule magnets and pseudocontact shift tags is a large magnetic anisotropy. In this article we present a dysprosium complex chemically designed to exhibit strong easy-axis type magnetic anisotropy that is preserved in dichloromethane solution at room temperature. Our detailed theoretical and experimental studies on the magnetic properties allowed explaining several features typical of highly performant SMMs.

Crystal structures of 3-halo-2-organochalcogenylbenzo[]chalcogenophenes.

The structure of the title compounds 3-bromo-2-(phenyl-sulfan-yl)benzo[]thiophene (CHBrS; ), 3-iodo-2-(phenyl-sulfan-yl)benzo[]thio-phene (CHIS; ), 3-bromo-2-(phenyl-selan-yl)benzo[]seleno-phene (CHBrSe; ), and 3-iodo-2-(phenyl-selan-yl)benzo[]seleno-phene (CHISe; ) were determined by single-crystal X-ray diffraction; all structures presented monoclinic (2/) symmetry. The phenyl group is distant from the halogen atom to minimize the steric hindrance repulsion for all structures. Moreover, the structures of and show an almost linear alignment of halogen-selenium-carbon atoms arising from the intra-molecular orbital inter-action between a lone pair of electrons on the halogen atom and the anti-bonding σ* orbital ( →σ*).

Polyoxovanadates as new P-glycoprotein inhibitors: insights into the mechanism of inhibition.

A promising strategy to overcome multidrug resistance is the use of inhibitors of ABC drug transporters. For this reason, we evaluated the polyoxovanadates (POVs) [V O ] (V ), [H V O (PO )] (V ), [V O Cl] (V ) and [V O I] (V ) as inhibitors of three major multidrug resistance-linked ABC transporters: P-glycoprotein (P-gp), ABCG2 and MRP1. All of the POVs selectively inhibited P-gp.

Stability in solution and chemoprotection by octadecavanadates(IV/V) in E. coli cultures.

Two mixed-valence octadecavanadates, (NH)(MeN)[VVOI]·MeNI·5HO (VI) and [{K(OH)VVO(PO)·4HO}] (VP), were synthesized and characterized by single-crystal X-ray diffraction analysis and FTIR, Raman, V NMR, EPR and UV/Vis/NIR spectroscopies. The chemoprotective activity of VI and VP towards the alkylating agent diethyl sulfate was assessed in E. coli cultures.

Seven-Coordinate Tb Complexes with 90% Quantum Yields: High-Performance Examples of Combined Singlet- and Triplet-to-Tb Energy-Transfer Pathways.

Seven-coordinate, pentagonal-bipyramidal (PBP) complexes [Ln(bbpen)Cl] and [Ln(bbppn)Cl], in which Ln = Tb (products and ), Eu ( and ), and Gd ( and ), with bbpen = ,'-bis(2-oxidobenzyl)-,'-bis(pyridin-2-ylmethyl)ethylenediamine and bbppn = ,'-bis(2-oxidobenzyl)-,'-bis(pyridin-2-ylmethyl)-1,2-propanediamine, were synthesized and characterized by single-crystal X-ray diffraction analysis, alternating-current magnetic susceptibility measurements, and photoluminescence (steady-state and time-resolved) spectroscopy. Under a static magnetic field of 0.1 T, the Tb complexes and revealed single-ion-magnet behavior.

Exploring the Organometallic Route to Molecular Spin Qubits: The [CpTi(cot)] Case.

The coherence time of the 17-electron, mixed sandwich complex [CpTi(cot)], (η -cyclooctatetraene)(η -cyclopentadienyl)titanium, reaches 34 μs at 4.5 K in a frozen deuterated toluene solution. This is a remarkable coherence time for a highly protonated molecule.

An Oxalate-Bridged Copper(II) Complex Combining Monodentate Benzoate, 2,2'-bipyridine and Aqua Ligands: Synthesis, Crystal Structure and Investigation of Magnetic Properties.

A dinuclear copper(II) complex of formula [{Cu()()(OH)}(μ-)] () (where = 2,2'-bipyridine, = benzoate and = oxalate) was synthesised and characterised by diffractometric (powder and single-crystal XRD) and thermogravimetric (TG/DTG) analyses, spectroscopic techniques (IR, Raman, electron paramagnetic resonance spectroscopy (EPR) and electronic spectroscopy), magnetic measurements and density functional theory (DFT) calculations. The analysis of the crystal structure revealed that the oxalate ligand is in bis(bidentate) coordination mode between two copper(II) centres. The other four positions of the coordination environment of the copper(II) ion are occupied by one water molecule, a bidentate and a monodentate ligand.

Methyl Ester Functionalized Phenalenyl Arene- and Bipyridine-Ruthenium-Based Complexes for Electroactive Langmuir-Blodgett Films.

We report the synthesis of a new phenalenyl ligand, functionalized with a methyl ester electron withdrawing group, named 9-hydroxy-1-oxo-1 H-phenalen-5-methyl carboxylate (L), and the generated complexes [Ru(bpy)L]PF and [(η-CH)Ru(L)Cl]. Compounds were characterized by spectroscopic and X-ray diffraction methods, and their electrochemical behavior was investigated via cyclic voltammetry and UV-vis spectroelectrochemistry. The one-electron oxidized compounds have an unpaired electron located in the phenalenyl ring, as supported by theoretical calculations (DFT) and EPR results.

Crystal structures of binuclear complexes of gadolinium(III) and dysprosium(III) with oxalate bridges and chelating ,'-bis-(2-oxido-benz-yl)-,'-bis-(pyridin-2-ylmeth-yl)ethyl-enedi-amine (bbpen).

The reaction between mononuclear [(bbpen)Cl] [ = Gd or Dy; Hbbpen = ,'-bis-(2-hy-droxy-benz-yl)-,'-bis-(pyridin-2-ylmeth-yl)ethyl-enedi-amine, CHNO] and potassium oxalate monohydrate in water/methanol produced the solvated centrosymmetric isostructural binuclear (μ-oxalato)bis-{[,'-bis-(2-oxidobenzyl-κ)-,'-bis-(pyridin-2-ylmethyl-κ)ethyl-enedi-amine-κ ,']dilanthanide(III)}-methanol-water (1/4/4) complexes, [ (CHNO)(CO)]·4CHOH·4HO, with lanthanide(III) = gadolinium(III) ( = Gd) and dysprosium(III) ( = Dy), in high yields ( 70%) directly from the reaction mixtures. In both complexes, the lanthanide ion is eight-coordinate and adopts a distorted square-anti-prismatic coordination environment. The triclinic ( ) unit cell contains one dimeric unit together with four water and four methanol mol-ecules; in the final structural model, two of each type of solvating mol-ecule refine well.

Effects of Decavanadate Salts with Organic and Inorganic Cations on Escherichia coli, Giardia intestinalis, and Vero Cells.

Decavanadate salts with nicotinamide (3-pyridinecarboxamide, 3-pca) and isonicotinamide (4-pyridinecarboxamide, 4-pca) in both neutral and protonated forms, (3-Hpca)[HVO]·2HO·2(3-pca) (complex I) and (4-Hpca)[HVO]·2(4-pca) (complex II), have been synthesized and characterized by vibrational spectroscopy (infrared and Raman), thermogravimetric analysis (TGA), V NMR, and single-crystal X-ray diffraction analysis. The effects of sodium decavanadate (henceforth called NaV) and compounds I and II on Escherichia coli, Giardia intestinalis, and Vero (African green monkey epithelial kidney) cells were evaluated. Enhanced growth inhibitory activity against E.