Spin fluctuations in the light-induced high spin state of Cobalt valence tautomers

We present a study of the static magnetic properties and spin dynamics in Cobalt valence tautomers (VT), molecules where a low-spin (LS) to high-spin (HS) crossover driven by an intramolecular electron transfer can be controlled by the temperature, by the external pressure or by light irradiation. In the investigated complex, a LS-Co(III) ion bound to a dinegative organic ligand can be reversibly converted into the HS-Co(II) bound to a mononegative one. By combining magnetization measurements with Nuclear Magnetic Resonance (NMR) and Muon Spin Relaxation ({\mu}SR), we have investigated the static magnetic properties and the spin dynamics as a function of the temperature. Moreover, the effect of the external pressure as well as of the infrared light irradiation have been explored through magnetometry and NMR measurements to determine the spin dynamics of the HS state. The photoinduced HS state, which can have a lifetime of several hours below 30 K, is characterized by spin dynamics in the MHz range, which persist at least down to 10 K. The application of an external pressure causes a progressive increase of the LS-HS crossover, which reaches room temperature for pressures around 10 kbar

Structure and magnetic properties of two new lanthanide complexes with the 1-((E)-2-pyridinylmethylidene)semicarbazone ligand

Two novel semicarbazone-lanthanide(III) complexes were prepared and structurally characterized as [Ln (Hscpy)2 (NO3)2]NO3·MeOH (Ln = Gd and Tb; Hscpy = 1-((E)-2-pyridinylmethylidene)semicarbazone). The 4f metal ions experience deca-coordination geometry. Each molecular formula contains two neutral Hscpy molecules in the keto form coordinated through two nitrogen atoms and one oxygen atom, while two nitrate ligands are both coordinated in a chelate mode. The 1 + charge of the cation-complex is balanced by a nitrate anion. Extensive intermolecular hydrogen bonds are formed through the methanol solvate molecule, which acts both as a donor and an acceptor molecule. The chemical composition of the compounds was confirmed by high resolution mass spectra (ESI-MS); peaks at m/z = 122.07 and 148.05, assigned to the fragments C6H8N3+ and C7H6N3O+, respectively, are in agreement with the coordination of Hscpy. Alternating current magnetic susceptibility analysis was performed in the 10–10000 Hz range, and the terbium-complex showed slow relaxation of the magnetization when immersed in a static magnetic field of 1 kOe and 1.5 kOe, with an activation barrier to the relaxation (21.9(4) cm−1) among the highest found for ten-coordinated Tb(III) complexes. This behavior of slow relaxation of the magnetization is relevant as a memory effect regarding the development of Single Molecule Magnets (SMM)

Fluorescent Asymmetrically Cobalt-Tipped CdSe@CdS Core@Shell Nanorod Heterostructures Exhibiting Room-Temperature Ferromagnetic Behavior

A colloidal two-step seeded-growth approach has been devised to selectively synthesize three-component magnetic/semiconductor hybrid nanocrystals (HNCs) with a matchstick-like profile and tunable geometric parameters. The newly developed heterostructures individually comprise a single metallic Co head connected to either apexes of one rod-shaped section made of a CdSe core eccentrically embedded in a CdS shell. The specific topological arrangement realized arises from the peculiar anisotropic reactivity of the noncentrosymmetric CdSe@CdS core@shell nanorods that have been used as substrates to seed heterogeneous nucleation of Co in a surfactant-free environment from an organometallic precursor. The HNCs retain appreciable fluorescent emission in spite of photoexcited charge transfer from the semiconductor to the metal domain and exhibit unusual ferromagnetic-like behavior at room temperature

Supramolecular assembly of new heteropolymetalic molecules based on tetraiminodiphenolate macrocycle and hexacyanometallate anions: magnetostructural and spectroscopic properties

Herein we report on the synthesis, single crystal X-ray structure, spectroscopic and magnetic properties of [{Cu2(tidf)(H2O)}2(μ-CN)2Fe(CN)4]·6H2O (1), [Cu2(tidf)(H2O)2][Ni(CN)4] (2) and [Cu2(tidf)(H2O)2][Fe(CN)5NO]·H2O (3) (tidf = a Robson type macrocyclic ligand obtained on condensation of 2,6-diformyl-4-methylphenol and 1,3-diaminopropane). Complex (1) is pentanuclear; two paramagnetic dicopper(II) units are linked by a hexacyanoferrate(II) ion through two cyano-bridges. All compounds exhibit extensive, three-dimensional, supramolecular structures supported by classic hydrogen bonding between the coordinated aqua ligands, water molecules and cyano groups. Magnetism as a function of the temperature of complexes 1-3 is consistent with a strong antiferromagnetism with exchange parameters 2J estimated -783(29), -913(2), -905(1), respectively.CNPqFINEP (CT-Infra 03/2001)BBSR

Seven-coordinate Tb3+ complexes with 90% quantum yields: High-performance examples of combined singlet- and triplet-to-Tb3+ energy-transfer pathways

Seven-coordinate, pentagonal-bipyramidal (PBP) complexes [Ln(bbpen)Cl] and [Ln(bbppn)Cl], in which Ln = Tb3+ (products I and II), Eu3+ (III and IV), and Gd3+ (V and VI), with bbpen2- = N,N′-bis(2-oxidobenzyl)-N,N′-bis(pyridin-2-ylmethyl)ethylenediamine and bbppn2- = N,N′-bis(2-oxidobenzyl)-N,N′-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 Tb3+ complexes I and II revealed single-ion-magnet behavior. Also, upon excitation at 320 nm at 300 K, I and II presented very high absolute emission quantum yields (0.90 ± 0.09 and 0.92 ± 0.09, respectively), while the corresponding Eu3+ complexes III and IV showed no photoluminescence. Detailed theoretical calculations on the intramolecular energy-transfer rates for the Tb3+ products indicated that both singlet and triplet ligand excited states contribute efficiently to the overall emission performance. The expressive quantum yields, QLnL, measured for I and II in the solid state and a dichloromethane solution depend on the excitation wavelength, being higher at 320 nm. Such a dependence was rationalized by computing the intersystem crossing rates (WISC) and singlet fluorescence lifetimes (τS) related to the population dynamics of the S1 and T1 levels. Thin films of product II showed high air stability and photostability upon continuous UV illumination, which allowed their use as downshifting layers in a green light-emitting device (LED). The prototypes presented a luminous efficacy comparable with those found in commercial LED coatings, without requiring encapsulation or dispersion of II in host matrixes. The results indicate that the PBP environment determined by the ethylenediamine (en)-based ligands investigated in this work favors the outstanding optical properties in Tb3+ complexes. This work presents a comprehensive structural, chemical, and spectroscopic characterization of two Tb3+ complexes of mixed-donor, en-based ligands, focusing on their outstanding optical properties. They constitute good molecular examples in which both triplet and singlet excited states provide energy to the Tb3+ ion and lead to high values of QLnL

Temperature- and Light-Induced Spin Crossover Observed by X-ray Spectroscopy on Isolated Fe(II) Complexes on Gold

Using X-ray absorption techniques, we show that temperature- and light-induced spin crossover properties are conserved for a submonolayer of the [Fe(H2B(pz)2)2(2,2′-bipy)] complex evaporated onto a Au(111) surface. For a significant fraction of the molecules, we see changes in the absorption at the L2,3 edges that are consistent with those observed in bulk and thick film references. Assignment of these changes to spin crossover is further supported by multiplet calculations to simulate the X-ray absorption spectra. As others have observed in experiments on monolayer coverages, we find that many molecules in our submonolayer system remain pinned in one of the two spin states. Our results clearly demonstrate that temperature- and light-induced spin crossover is possible for isolated molecules on surfaces but that interactions with the surface may play a key role in determining when this can occur

Crystal Packing Effects on the Magnetic Slow Relaxation of Tb(III)-Nitronyl Nitroxide Radical Cyclic Dinuclear Clusters.

International audienceFour lanthanide-based nitronyl nitroxide radical cyclic molecular clusters of formula [Ln(hfac)(3)(NITPhPO(OEt)(2))](2) (Ln(III) = Gd (1), Tb (2A and 2B), and Dy (3) and NITPhPO(OEt)(2) = 4'-[2-(1-oxyl-3-4,4,5,5-tetramethylimidazoline)phenyl]diethoxylphosphine oxide) have been synthesized. Their X-ray structures have been solved and highlight two different crystal packings. For the particular case of the Tb(III) derivative, both of them can be obtained. In 2A, the molecules are well-isolated, while 2B shows short contacts between N-O radical groups. Static magnetic studies on the Gd(III) derivative (1) demonstrate that lanthanides and radicals are ferromagnetically coupled (J = 3.46 ± 0.04 cm(-1)). Dynamic magnetic studies show that both compounds 2A and 2B exhibit single molecule magnet behavior. A comparison of their magnetic behaviors highlights that the crystal packing has a crucial influence on the temperature range in which the SMM behavior is observed. In the case of the well-insulated Tb(III)-based derivative (2A), the SMM behavior is observed at higher temperatures and lower frequencies than for the one that presents close-packing between the molecules (2B). Comparisons are then possible only under an applied external magnetic field (0.2 T) with Δ = 27.5(6) and 21.0(5) K and τ(0) = 2.64(25) × 10(-9) and 1.76(20) × 10(-9) s for 2A and 2B, respectively

Magnetic relaxation in dysprosium and terbium 1D-zigzag coordination chains having only 4,4′-bipyridine as connector

The coordination chain {[Dy(dbm)(3)bpy]center dot C7H8}(n) (1) having only 4,4'-bipyridine as connector has been prepared in high yield and its structural and magnetic properties have been investigated. It is isostructural with the terbium analogue {[Dy(dbm)(3)bpy]center dot C7H8}(n) (2) and features units repeating in a 1D-zigzag fashion, where the metal is octa-coordinated in a distorted square antiprism geometry. Despite the 1D structure, the absence of paramagnetic connectors prevents the direct magnetic intrachain interaction among the lanthanide ions. In zero magnetic field, only a small fraction of the magnetization of 1 displayed slow dynamics with no dependence on temperature. Upon application of a 1 kOe magnetic field, a relaxation process appears, compatible with a mixed Raman/Direct mechanisms. Magnetic dilution in the diamagnetic Y(III)-based analogue revealed that actually two distinct relaxation processes are active for 1, whose temperature dependence can be interpreted again with a mixed Raman/Direct relaxation model. Compound 2 displayed only in-field slow relaxation, compatible with the models employed for 1