Tuning the Magnetoluminescence Behavior of Lanthanide Complexes Having Sphenocorona and Cubic Coordination Geometries

Abstract

Abstract:The reaction of the tripodal fluorophoric ligand tris(benzimidazol-2-ylmethyl)amine (ntbi) with two different lanthanide salts [Ln(NO 3 ) 3 and LnCl 3 (Ln = Dy, Ho, Tb)] afforded two new classes of mononuclear complexes. The class 1 complexes [{Ln(ntbi)(NO 3 ) 3 } 2 ·3CH 3 OH; Ln = Dy (1) and Ho (3)] exhibit very rare "sphenocorona" coordination geometries around the Ln centers, whereas the class 2 complexes [{Ln(ntbi) 2 } 5 · 15Cl·xH 2 O; Ln = Dy, x = 18 (2) and Ln = Tb, x = 27 (4)] show

Slow Magnetic Relaxation in Lanthanoid Crown Ether Complexes: Interplay of Raman and Anomalous Phonon Bottleneck Processes

“…The lanthanoid centers in 1‐Ln are 10‐coordinate for all complexes. Continuous shape measurements performed with the Shape 2.1 software suggest that the coordination geometry is best described as a sphenocorona (Figure and Table S4), with approximate C 2 v point symmetry, which is among the rarest for 10‐coordinated lanthanoid species . The Shape distortion parameters for 1‐Ln are in the range 2.104–3.015, where the further the value is from zero, the greater the distortion from ideal geometry.…”

Vertical‐Aligned Li2S–Graphene Encapsulated within a Carbon Shell as a Free‐Standing Cathode for Lithium–Sulfur Batteries

“…The lanthanoid centers in 1-Ln are 10-coordinatefor all complexes.C ontinuous shape measurements performed with the Shape 2.1 software [27] suggest that the coordination geometry is best described as as phenocorona (Figure 1a nd Ta bleS4), with approximate C 2v point symmetry,w hich is among the rarest for 10-coordinated lanthanoid species. [28] TheS hape distortionp arameters for 1-Ln are in the range 2.104-3.015, where the further the value is from zero, the greater the distortion from ideal geometry.T he six Oa toms from the crownether occupy the nominal( bent) equatorial plane and the four Oa toms from the catecholate and nitrate ligands occupy the axial sites. Due to the difference in steric hindrance of the two apical ligands, the crown ether showsadistortion towardt he nitrate anion and the eclipsed disposition of the axial ligands is characterized by ad ihedrala ngle of 77.68(5)8 between the two respective planes of inclusion.…”

Heteroleptic Lanthanide Complexes Coordinated by Tripodal Tetradentate Ligand: Synthesis, Structure, and Magnetic and Photoluminescent Properties

“…In addition, these ligands present also an interesting potential with the aim to introduce others functionalities besides magnetism, such as luminescence or redox activity. 36,37 However, to the best of our knowledge, examples of lanthanide complexes based on such ligands are relatively scarce, 34 while only a few lanthanide SMMs based on the tripodal C 3 tren ligand derivatives such as Schiff bases have been published. [38][39][40][41] Following this, we report in this article the synthesis, structures, magnetic and photoluminescent properties of a series of lanthanide ion complexes based on an original tripodal tetradentate Tmpa ligand.…”