A new family of lanthanide complexes, [Ln2(hfac)4L2] (Ln = Eu (1), Gd (2), Tb (3), Dy (4), Ho (5), Er (6), Lu (7); hfac = hexafluoroacetylacetonate, HL = 2-(2′-benzothiazole)-8-hydroxyquinoline), was synthesized and characterized using single-crystal X-ray diffraction, elemental analysis (EA), thermal gravimetric analysis (TGA), powder X-ray diffraction (PXRD) and UV-vis spectra. X-ray crystallographic analyses reveal that 1–7 are isomorphous and crystallize in the monoclinic space group C2/c. In these dinuclear complexes, each LnШ ion is eight-coordinated with two bidentate hfac and two μ-phenol bridging L ligands. The TGA results show that the complexes have relatively high thermal stabilities. Complexes 1 and 3 show the characteristic transitions of the corresponding lanthanide ions with ligand-related emission peaks. Meanwhile, complexes 4 and 7 exhibit ligand-centered fluorescence at room temperature. Magnetic measurements were carried out on complexes 2–6. The magnetic study reveals that 2 displays a magnetocaloric effect, with a maximum −ΔSm value of 16.89 J K−1 kg−1 at 2 K for ΔH = 8 T. Dynamic magnetic studies reveal single-molecule magnet (SMM) behavior for complex 4. Fitting the dynamic magnetic data to the Arrhenius law gives an energy barrier ΔE/kB = 50.33 K and pre-exponential factor τ0 = 1.05 × 10(-8)s.
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http://dx.doi.org/10.1039/c5dt02894a | DOI Listing |
Inorg Chem
December 2024
Institute of Nano Science and Technology, Sector-81, Mohali, Punjab 140306, India.
Among lanthanide-based single-molecule magnets (SMMs), erbium(III) is a Kramers ion, apart from dysprosium(III), which provides magnetic bistability in the presence of a suitable coordination environment. However, Er-based SMMs exhibit significantly less magnetic anisotropy than Dy because their prolate electronic density necessitates equatorially correlated ligands to minimize the charge contact with the Er atom. Here, in this work, we have computationally investigated the heteroleptic organometallic complexes with an Er(III) atom sandwiched between two distinct cyclic rings (five- and eight-membered) with the aim of tuning the magnetic anisotropy via exploiting the ligand field.
View Article and Find Full Text PDFACS Sens
December 2024
School of Mechanical Engineering, Southeast University, Nanjing 211189, People's Republic of China.
Background noise interferes with the accurate detection of early tumor biomarkers. This study introduces a method that effectively reduces background noise to enhance detection accuracy by combining a color-coded signaling approach with the unique fluorescent properties and room-temperature tunable quantum spin characteristics of fluorescent diamonds (FNDs) with nitrogen-vacancy centers. In this approach, a red signal indicates the presence of the target analyte within the spectral region, a green signal indicates its absence, and a yellow signal indicates the need for further analysis using FNDs' quantum spin properties for optical detection magnetic resonance (ODMR) to distinguish the FND signal from background noise.
View Article and Find Full Text PDFUnlabelled: Molecular crowding influences DNA mechanics and DNA - protein interactions and is ubiquitous in living cells. Quantifying the effects of molecular crowding on DNA supercoiling is essential to relating experiments to DNA supercoiling. We use single molecule magnetic tweezers to study DNA supercoiling in the presence of dehydrating or crowding co-solutes.
View Article and Find Full Text PDFJ Phys Chem A
December 2024
Department of Chemical and Materials Engineering, University of Nevada Reno, Reno, Nevada 89557, United States.
Single-molecule magnets (SMMs) with slow relaxation of magnetization and blocking temperatures above that of liquid nitrogen are essential for practical applications in high-density data storage devices and quantum computers. A rapid and accurate prediction of the effective magnetic relaxation barrier () is needed to accelerate the discovery of high-performance SMMs. Using density functional theory and multireference calculations, we explored correlations between , partial atomic charges, and the anisotropic barrier for a series of sandwich-type lanthanide complexes containing cyclooctatetraene, substituted cyclopentadiene, phospholyl, boratabenzene, or borane ligands.
View Article and Find Full Text PDFInorg Chem
December 2024
Physical Institute, Karlsruhe Institut of Technology (KIT) Campus South, Wolfgang-Gaede-Str. 1, Karlsruhe 76131, Germany.
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.
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