Chemistry of lanthanons—XVII: Bis-salicylaldehyde ethylenediamine and bis-salicylaldehyde o-phenylenediamine complexes of rare-earths

doi:10.1016/0022-1902(68)80263-5

Journal of Inorganic and Nuclear Chemistry

Volume 30, Issue 9, September 1968, Pages 2493-2499

https://doi.org/10.1016/0022-1902(68)80263-5 Get rights and content

Abstract

A new series of rare-earth metal chelates derived from N-coordinating ligands like bis-salicylaldehyde ethylenediamine (H₂Salen) and bis-salicylaldehyde o-phenylenediamine (H₂Salphen) have been prepared with La, Ce, Pr, Nd, Sm, Gd, Dy, Er, Yb and Y. These compounds are of the general formula Ln₂(Salen)₃ and Ln₂(Salphen)₃ (where Ln stands for the above lanthanides except Ce). The cerium complex prepared with H₂Salen has the composition Ce(Salen)₂. Many compounds of the former series are solvated and contain ethanol or water molecules. These compounds have been characterised by their thermal analyses and i.r. spectra.

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An appropriate amount of BSA was dissolved in water to obtain a BSA solution (1.5 × 10-4 mol/L) and stored in the refrigerator. Bis(salicylaldehyde)-o-phenylenediamine (SALOPHEN) was prepared according to the method reported by N.K. Duttl [27]. Synthetic routes and characterization diagrams are shown in Fig. S1 (Supporting information).
A compound generally has only a single maximum emission wavelength. Therefore, it is relatively difficult to construct a dual-output molecular logic circuit. Herein, a novel fluorescent probe is designed by combining BSA and N, N′-bis(salicylidene)-ethylenediamine. The fluorescence intensity of the probe significantly fluorescence responses at 350 nm or 440 nm changed when stimulated with Zn²⁺, Fe²⁺, Cu²⁺, and EDTAH₂Na₂. Consequently, three different functional dual-output digit logic circuits are successfully designed in an aqueous solution. This combination is versatile with an additional advantage of water-solubility. Simultaneously, this combination provides a good reference model in exploring Dexter energy transfer in fluorescent experiments.
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Neither PEI nor low molecular amines complex formation with Ce ions has been reported in the literature. The lack of N-coordinated complexes of the rare-earths in water was ascribed partly to the fact that nitrogen-donating ligands would form less stable complexes with these elements, and also to the fact that such ligands, being basic in nature, would precipitate hydroxides of these metals from their solutions [37]. However, formation of ethylenediamine, diethylenetriamine and triaminotriethylamine chelates of the tripositive lanthanide ions in a non-aqueous dry solvent, i.e. acetonitrile, have been reported in the literature [38,39].
A novel templating strategy for the development of composite nanoporous CuO/CeO₂/SiO₂ materials with advanced properties and significant thermal stability is proposed in this work, for potential use in automotive catalysts. The synthetic process is based on the dual role of low cost hyperbranched polyethyleneimine (PEI) acting both as a reactive template to control the formation of a siliceous porous network and as a metal chelating agent to facilitate the incorporation of finely dispersed CuO/CeO₂ nanoparticles into the silica matrix. Direct Ce(III)/Cu(II) introduction into the reaction mixture or post-synthetic impregnation of a preformed hybrid organic/inorganic xerogel was employed. Materials properties were assessed by means of XRD, SEM, TEM, N₂ adsorption, TPR and XPS techniques. Final Cu loading was determined by a novel UV–Vis spectroscopic method. Activity tests were performed under stoichiometric, O₂-deficient and O₂-rich conditions simulating realistic exhaust environment. Catalytic performance was found to be strongly depended on the employed synthetic pathway. The CuO/CeO₂/SiO₂ composites prepared by direct introduction, exhibited enhanced structural characteristics (BET ≈ 680 m²/g), high homogeneity, superior oxidation performance and notable thermal stability, with great potential for use in automotive aftertreatment systems.
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In exploring relevant double-decker and triple-decker complexes, the salen-type ligand H2dsp, attracted our eyes as well. The synthesis of complexes [Ln2(dsp)3(Sol)] (Sol is the coordinate solvent molecule) can be traced back to the year 1968 [25]. Both [Ln(dsp)2]− and [Ln2(dsp)3(Sol)] were spectrally characterized in 1994 [26].
We report on the synthesis of two dysprosium(III) containing complexes with double-decker and triple-decker sandwich structures. These two complexes have formulae (NMe₄)[Dy(dsp)₂] (1) and [Dy₂(dsp)₃(EtOH)] (2), where H₂dsp is a salen type ligand. Both compounds were characterized by X-ray structural analysis, UV–Vis, IR spectral and magnetic studies. Complex 1 crystallized in the space group Pna2₁. This X-ray structural data provides the first example of the structure of [Ln(dsp)₂]⁻. Compound 2 crystallized in a triclinic space group $P \bar{1}$ . In both cases, two similar but symmetry-independent molecules are present. The UV–Vis spectra of the complexes indicate that they are ligand-based π–π^∗ transitions, which was further supported by DFT calculations. Both compounds display field-induced out-of-phase signals. In particular, step-wise slow magnetization relaxation processes are observed in the case of complex 2. This indicates that compound 1 and 2 undergo slow magnetization relaxation when a small dc magnetic field is applied.
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In this section, we describe the formation and properties of ten polynuclear lanthanide complexes (1–10) with H2salen (H2L1) and H2L2–3 ligands. Complexes formed by Ln(III) with H2salen were reported as early as 1968 [31]. For example, some mononuclear, dinuclear and tetranuclear lanthanide complexes with formations of Ln/(ligand)1–3 [32], Ln2/(ligand)2–3 [33–35], and Ln4/(ligand)6 [36] (ligand = H2L1 or L1) have been reported.
The synthesis, crystal structures and photophysical properties of thirty-one 4f and d-4f polynuclear complexes and coordination polymers based on nine flexible salen-type ligands are described in this review. Most of these lanthanide complexes exhibit either interesting “twisted”, drum-like or polymeric structures. In these complexes, the multidentate salen-type ligands can efficiently sensitize lanthanide emissions by serving as antennas that absorb excitation light and transfer the energy to the lanthanide centers. With the lanthanide ions encapsulated by chromophoric salen-type ligands and shielded from solvent molecules which can quench the emissions from lanthanide ions, those lanthanide complexes which have “twisted” and drum-like structures show impressive luminescence properties.
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Nitrate is often shown to be coordinated in a bidentate chelate fashion, allowing the lanthanide ion to easily achieve high coordination number [8]. Lanthanide complexes with salicylaldimine Schiff base, in particular, have been the subject of intense current research [48–59]. Potentially bidentate though, common binding mode of these type Schiff base ligands involves zwitterionic monodentate coordination via deprotonated phenolic-oxygen with the proton shifted to imine–nitrogen [5–8,56].
A series of new mononuclear lanthanide(III)-salicylaldimine complexes of the type [Ln(LH)₃(NO₃)₃] (Ln = La, Pr, Sm and Gd; LH = N-(2-hydroxyethyl)-4n-alkoxysalicylaldimine, n = 14, 18) have been synthesized and characterized by FT-IR, ¹H NMR, ¹³C NMR, UV–Vis, FAB-mass and magnetic susceptibility measurements. The ligand (LH) coordinate to lanthanide ions in zwitterionic form via the phenolic-oxygen with the proton shifted to the imine–nitrogen. The nitrato groups occurring in chelated bidentate fashion complete a nine-coordinate geometry. Polarized optical microscopy (POM) and differential scanning calorimetry (DSC) show that the ligands are monotropic and their complexes exhibit enantiotropic highly viscous smectic A (SmA) mesophase in the temperature range 60–185 °C. A bilayer self organized assembly of the molecules in the mesophase are proposed on the basis of the small angle XRD study. The ligands are blue light emitters with a broad emission maxima at ∼447 nm while the lanthanide complexes show intense emission in the visible range (∼465–679 nm) at 350 nm excitation. The samarium(III) complex, [Sm(LH)₃(NO₃)₃] is distinct from the rest in emitting bright orange light (∼660 nm, Φ = 48%). The S_o–S₁ excitation band being stronger than the direct f–f excitation in the samarium complex clearly suggests that the Schiff-base ligands efficiently sensitize the luminescence of Sm³⁺. DFT calculations have been performed using DMol3 program at BLYP/DNP level to obtain the stable electronic structure of the ligand and complex.
A novel di-iron(III) structure based on an ageless ligand
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Salen-type Schiff base ligands possess a N₂O₂ coordination site able to chelate transition metal ions. Reaction of such a ligand with FeCl₃·6H₂O leads to the formation of a genuine dinuclear L₃Fe₂ complex in which the ligand plays a double role. The structural determination confirms that each iron ion is wrapped up by a chelating tetradentate ligand while the third one ensures a bridge in between the two Fe ions and completes to six the metal coordination sphere. Such a bridge implies a non planar coordination of the chelating ligands and induces helicity around each metal ion. Crystals are true racemates made of homochiral Λ–Λ and Δ–Δ pairs. The magnetic study confirms the absence of a spin exchange interaction through the saturated diamino chain and the presence of an axial single ion zero field splitting (ZFS) D equal to −0.7 cm⁻¹. The Mössbauer spectra show a unique asymmetric quadrupole-split doublet with isomer shift values, δ, of 0.342(2), 0.438(2) and 0.450(2) mm s⁻¹, and quadrupole splittings, ΔE_Q, of 0.826(4), 0.836(4) and 0.827(4) mm s⁻¹ at 293, 80 and 4.5 K, respectively. These values are in agreement with a high-spin iron(III) site in a N₃O₃ ligand environment.

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Chemistry of lanthanons—XVII: Bis-salicylaldehyde ethylenediamine and bis-salicylaldehyde o-phenylenediamine complexes of rare-earths

Abstract

Anal. chim. acta

Spectrochim. Acta

J. inorg. nucl. Chem.

J. inorg. nucl. Chem.

Chem. Rev.

Inorg. Chem.

Inorg. Chem.