Dinuclear fluoride single-bridged lanthanoid complexes as molecule magnets: unprecedented coupling constant in a fluoride-bridged gadolinium compound

A new synthetic method allows isolating fluoride-bridged complexes Bu4N{[M(3NO2,5Br-H3L1,1,4)]2(μ-F)} (M = Dy, 1; M = Ho, 2; M = Gd, 3) and Bu4N{[Dy(3Br,5Cl-H3L1,2,4)]2(μ-F)}·2H2O, 4·2H2O. The crystal structures of 1·5CH3C6H5,·2·2H2O·0.75THF, 3, and 4·2H2O·2THF show that all of them are dinuclear compounds with linear single fluoride bridges and octacoordinated metal centers. Magnetic susceptibility measurements in the temperature range of 2–300 K reveal that the GdIII ions in 3 are weakly antiferromagnetically coupled, and this constitutes the first crystallographically and magnetically analyzed gadolinium complex with a fluoride bridge. Variable-temperature magnetization demonstrates a poor magnetocaloric effect for 3. Alternating current magnetic measurements for 1, 2, and 4·2H2O bring to light that 4·2H2O is an SMM, 1 shows an SMM-like behavior under a magnetic field of 600 Oe, while 2 does not show relaxation of the magnetization even under an applied magnetic field. In spite of this, 2 is the first fluoride-bridged holmium complex magnetically analyzed. DFT and ab initio calculations support the experimental magnetic results and show that apparently small structural differences between 1 and 4·2H2O introduce important changes in the dipolar interactions, from antiferromagnetic in 1 to ferromagnetic in 4·2H2OThe authors thank the Spanish Ministerio de Ciencia e Innovación projects (PGC2018-102052-B-C21, PGC2018-093863-B-C21, MCIN/AEI/10.13039/501100011033/FEDER “Una manera de hacer Europa”) for financial support. E.C. acknowledges Junta de Andalucía for the FEDER Andalucía project A-FQM-172-UGR18. J.C.-V. also thanks Xunta de Galicia for his Ph.D. fellowship (ED481A-2018/136)S

An Easy Approach to Obtain Alcohol-Amines by Reduction of Alcohol Functionalized Imines

The reduction of functionalized imines to yield amines is often an intricate task, since most of the methods described in the literature to reduce imines to amines do not take into account that many reducing agents have also basic character. In this way, iminic compounds that have phenol functions usually produce the phenolic salt of the precursor when they are treated with a basic reducing agent, but not the desired amine. In this work, we describe an easy way of isolating very pure aminic compounds with alcoholic functions in its structure from the corresponding iminic compounds, by using NaBH4 as a reducing agent, and avoiding tedious chromatography or multiple solvent extraction steps

2D Supramolecular Structure for a Chiral Heterotrinuclear ZnII2HoIII Complex through Varied HBonds Connecting Solvates and Counterions

We report the crystal structure of [ZnII2HoIII(L)(ald)(HO)(H2O)3(MeCN)](NO3)2·EtOH [H3L = 2-(5-bromo-2-hydroxy-3-methoxyphenyl)-1,3-bis[4-(5-bromo-2-hydroxy-3-methoxyphenyl)-3-azabut-3-enyl]-1,3-imidazolidine) and Hald = 5-bromo-2-hydroxy-3-methoxy-benzaldehyde]. Despite the presence of two bulky multidentate ligands, as well as several monodentate ligands surrounding the nonacoordinate holmium cation, and the two pseudooctahedral zinc ions, the intricate H-bonded system formed by this chiral heterotrinuclear complex is only expanded in a 2D supramolecular structure. The interactions involve the nitrate counterions and the solvated ethanol, in such way that each complex unit is connected to an identical enantiomer, and to two units of inverted chirality through H bonds

Rearrangement of Imidazolidine to Piperazine Rings in the Presence of Dy^III

The formation of imidazolidines from secondary amines and aldehydes is well known. This small cycle can act as a nitrogen donor, and it is usually stable when it coordinates to metal ions. Sometimes, imidazolidines acting as ligands undergo breaking of the C-N bond when coordinating to the metal center, yielding related amines. However, the reorganization of the imidazolidine into a piperazine ring is quite an unusual process. In this work, we describe the transformation of a zinc complex with a ligand containing two imidazolidine moieties into a zinc complex with a piperazine fragment as donor, in the presence of a dysprosium salt

Filling Tricompartmental Ligands with Gd^III and Zn^II Ions: Some Structural and MRI Studies

Here we report the synthesis and characterization of a mononuclear gadolinium complex (Gd) and two heteronuclear Zn-Gd complexes (ZnGd and Zn2Gd), which contain two similar three-armed ligands that display an external compartment suitable for lanthanoid ions, and two internal compartments adequate for zinc (II) ions [H3L′ = (2-(3-formyl-2-hydroxy-5-methyl phenyl)-1,3-bis[4 -(3-formyl-2-hydroxy-5-methylphenyl)-3-azabut-3-enyl]-1,3-imidazolidine; H3L = 2-(5-bromo-2-hydroxy-3-methoxyphenyl)-1,3-bis[4-(5-bromo-2-hydroxy-3-methoxyphenyl)-3-azabut-3-enyl]-1,3-imidazolidine]. The synthetic methods used were varied, but the use of a metalloligand, [Zn2(L)AcO], as starting material was the key factor to obtain the heterotrinuclear complex Zn2Gd. The structure of the precursor dinuclear zinc complex is mostly preserved in this complex, since it is based on a compact [Zn2Ln(L)(OH)(H2O)]3+ residue, with a µ3-OH bridge between the three metal centers, which are almost forming an isosceles triangle. The asymmetric spatial arrangement of other ancillary ligands leads to chirality, what contrasts with the totally symmetric mononuclear gadolinium complex Gd. These features were confirmed by the crystal structures of both complexes. Despite the presence of the bulky compartmental Schiff base ligand, the chiral heterotrinuclear complex forms an intricate network which is predominately expanded in two dimensions, through varied H-bonds that connect not only the ancillary ligands, but also the nitrate counterions and some solvated molecules. In addition, some preliminary magnetic resonance imaging (MRI) studies have been made to determine the relaxivities of the three gadolinium complexes, with apparently improved T1 and T2 relaxivities with increasing zinc nuclearity, since both transversal and longitudinal relaxivities appear to enhance in the sequence Gd < ZnGd < Zn2Gd

Evaluation of the antimicrobial activity of some chloro complexes of imidazole-2-carbaldehyde semicarbazone: X-ray crystal structure of cis-NiCl2(H2L)(H2O)

Some first row transition metal(II) complexes of imidazole-2-carbaldehyde semicarbazone (H2L) have been synthesised and characterised. Single crystal X-ray diffraction studies have revealed the molecular structure of the neutral complex NiCl2(H2L)(H2O). This latter complex shows a pseudo-octahedral geometry, with both chloride ions displaying a cis disposition. The asymmetry of this complex allows the formation of two enantiomers in the racemic crystal structure. The non-deprotonated semicarbazone ligand behaves as an N,N,O-donor, through the imidazole and imine N atoms and the Oketo atom. The coordinative behaviour of H2L in CuCl2(H2L)(H2O), ZnCl2(H2L)20.5EtOH and CoCl2(H2L)20.5H2O is reported as only N,O-donor. The antimicrobial activity of the semicarbazone ligand and its metal complexes has been tested against some representative bacteria and fungi. A moderate inhibitory activity of the cobalt complex was detected towards the assayed phytopathogenic fungi Alternaria tenuis and Sclerotinia minor (MIC 50 microg/mL)

Rearrangement of Imidazolidine to Piperazine Rings in the Presence of DyIII

The formation of imidazolidines from secondary amines and aldehydes is well known. This small cycle can act as a nitrogen donor, and it is usually stable when it coordinates to metal ions. Sometimes, imidazolidines acting as ligands undergo breaking of the C-N bond when coordinating to the metal center, yielding related amines. However, the reorganization of the imidazolidine into a piperazine ring is quite an unusual process. In this work, we describe the transformation of a zinc complex with a ligand containing two imidazolidine moieties into a zinc complex with a piperazine fragment as donor, in the presence of a dysprosium salt

Detecting CdSe Nanomaterials with a Fluorescent Schiff Base Ligand

We investigated the easily synthesized ligand H3L as a fluorescent chemosensor for the detection of CdSe nanoparticles (CdSe NPs) and L-cysteine-capped CdSe quantum dots (CdSe-Cys QDs) in ethanol–water samples. A drastic quenching of the fluorescence emission of H3L at 510 nm occurred, as a result of the addition of CdSe NPs and CdSe-Cys QDs. A solution of H3L (1.26 ppb) showed sensitive responses to both CdSe NPs and CdSe-Cys QDs, with limits of detection (LOD) as low as 40 and 62 ppb, respectively. Moreover, using a smartphone color recognizer application, the fluorescence intensity response of H3L-modified cellulose paper to CdSe-Cys QDs was recorded on a red channel (R), which allowed us to detect CdSe-Cys QDs with LOD = 15 ppb. Interference of some common metal nanomaterials (NMs), as well as metal ions, in the determination of CdSe NMs in solution was studied. The affinity of H3L to CdSe NPs and CdSe-Cys QDs was spectroscopically determined. Scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM/EDX), micro-X-ray fluorescence (µ-XRF), 1H-NMR, attenuated total reflection infrared spectroscopy (ATR-IR), and density functional theory (DFT) were also used to investigate the interaction of H3L with CdSe NMs

Lanthanoid complexes of pentadentate and hexadentate N5 and N6 macrocycles: synthesis and applications

In this paper, the lanthanoid complexes of N5 and N6 macrocycle ligands, without pendant arms or additional heteroatoms, are surveyed. This review covers the period from 2015 to the current date, since in 2014 Schiff base macrocyclic ligands incorporating the pyridine moiety, and their complexes, were revised, and in 2015 the chemistry of pentaaza macrocycle ligands with rare earth metals was also summarized. Porphyrin and phthalocyanine ligands are not included in this review, which primarily focuses on complexes with Schiff bases and amines without pendant arms or any additional donor other than nitrogen. The synthetic methods, structural characterization, based on single X-ray crystal data, and properties of the lanthanoid complexes, with special attention to magneto-structural correlations, are presented herein.publishe