The effect of terminal N-donor aromatic ligands on sensitization and emission of lanthanide ions in Zn2Ln (Ln = Eu, Tb) complexes with 4-biphenylcarboxylate anions

2021 ◽  
Author(s):  
Stanislav N. Melnikov ◽  
Igor Evstifeev ◽  
Stanislav A. Nikolaevskii ◽  
Ivan V. Ananyev ◽  
Evgenia Varaksina ◽  
...  
Keyword(s):  
General Formula ◽  
Molecular Complexes ◽  
Lanthanide Ions ◽  
Biphenylcarboxylic Acid

The systematical series of Zn-Ln trinuclear carboxylate molecular complexes with general formula [Zn2Ln(NO3)(phbz)6(L)2] (Ln = Eu, Gd, Tb; phbz is anion of 4-biphenylcarboxylic acid; L is pyridine, 2,3-lutidine or 2,2’-bipyridine)...

scholarly journals Design, Isolation, and Spectroscopic Analysis of a Tetravalent Terbium Complex

2019 ◽  
Author(s):  
Natalie Rice ◽  
Ivan Popov ◽  
Dominic Russo ◽  
John Bacsa ◽  
Enrique Batista ◽  
...  
Keyword(s):  
Ground State ◽  
Molecular Complexes ◽  
Lanthanide Ions ◽  
Ligand Field ◽  
Zero Field ◽  
High Symmetry ◽  
Zero Field Splitting ◽  
Terbium Complex ◽  
Field Splitting ◽  
Metal Ligand

Synthetic strategies to yield molecular complexes of high-valent lanthanides, other than the ubiquitous Ce<sup>4+</sup> ion, are exceptionally rare, and thorough, detailed characterization in these systems is limited by complex lifetime and reaction and isolation conditions. The synthesis of high-symmetry complexes in high purity with significant lifetimes in solution and solid-state are essential for determining the role of ligand-field splitting, multiconfigurational behavior, and covalency in governing the reactivity and physical properties of these potentially technologically transformative tetravalent ions. We report the synthesis and physical characterization of an <i>S</i><sub>4</sub> symmetric, four-coordinate tetravalent terbium complex, [Tb(NP(1,2-bis-<i><sup>t</sup></i>Bu-diamidoethane)(NEt<sub>2</sub>))<sub>4</sub>] (where Et is ethyl and <i>t</i>Bu is <i>tert</i>-butyl). The ligand field in this complex is weak and the metal-ligand bonds sufficiently covalent so that the tetravalent terbium ion is stable and accessible via a mild oxidant from the anionic, trivalent, terbium precursor, [(Et<sub>2</sub>O)K][Tb(NP(1,2-bis-<i><sup>t</sup></i>Bu-diamidoethane)(NEt<sub>2</sub>))<sub>4</sub>]. The significant stability of the tetravalent complex enables its thorough characterization. The step-wise development of the supporting ligand points to key ligand control elements for further extending the known tetravalent lanthanide ions in molecular complexes. Magnetic susceptibility, electron paramagnetic resonance (EPR) spectroscopy, X-ray absorption near-edge spectroscopy (XAS), and density functional theory studies indicate a <i>4f<sup>7</sup></i> ground state for [Tb(NP(1,2-bis-<i><sup>t</sup></i>Bu-diamidoethane)(NEt<sub>2</sub>))<sub>4</sub>] with considerable zero-field splitting: demonstrating that magnetic, tetravalent lanthanide ions engage in covalent metal-ligand bonds. This result has significant implications for the use of tetravalent lanthanide ions in magnetic applications since the observed zero-field splitting is intermediate between that observed for the trivalent lanthanides and for the transition metals. The similarity of the multiconfigurational behavior in the ground state of [Tb(NP(1,2-bis-<i><sup>t</sup></i>Bu-diamidoethane)(NEt<sub>2</sub>))<sub>4</sub>] (measured by Tb L<sub>3</sub>-edge XAS) to that observed in TbO<sub>2</sub> implicates ligand control of multiconfigurational behavior as a key component of the stability of the complex.

scholarly journals The Utility of 2,2′-Bipyrimidine in Lanthanide Chemistry: From Materials Synthesis to Structural and Physical Properties

2011 ◽  
Vol 2011 ◽  
pp. 1-13 ◽  
Author(s):  
Gaël Zucchi
Keyword(s):  
Magnetic Properties ◽  
Solid State ◽  
Physical Properties ◽  
Coordination Mode ◽  
Molecular Complexes ◽  
Structural Chemistry ◽  
Lanthanide Ions ◽  
Neutral Ligand ◽  
Materials Synthesis ◽  
Lanthanide Chemistry

This paper reviews the recent investigations undertaken on the use of 2,2′-bipyrimidine (bpm) as a ligand for designing molecular complexes as well as polymeric lanthanide materials. A special emphasis is put on the ability of this polydentate neutral ligand to yield compounds of various dimensionalities, to act as a connector between these large ions, and influence their emissive and magnetic properties. This ligand can adopt a terminal or a bridging coordination mode with lanthanide ions, thus generating a wealth of frameworks of various topologies with the 4f elements. The main focus of this review is to show the originality brought by bpm in lanthanide structural chemistry and solid-state photophysics and magnetism.

scholarly journals Design, Isolation, and Spectroscopic Analysis of a Tetravalent Terbium Complex

2019 ◽  
Author(s):  
Natalie Rice ◽  
Ivan Popov ◽  
Dominic Russo ◽  
John Bacsa ◽  
Enrique Batista ◽  
...  
Keyword(s):  
Ground State ◽  
Molecular Complexes ◽  
Lanthanide Ions ◽  
Ligand Field ◽  
Zero Field ◽  
High Symmetry ◽  
Zero Field Splitting ◽  
Terbium Complex ◽  
Field Splitting ◽  
Metal Ligand

Synthetic strategies to yield molecular complexes of high-valent lanthanides, other than the ubiquitous Ce<sup>4+</sup> ion, are exceptionally rare, and thorough, detailed characterization in these systems is limited by complex lifetime and reaction and isolation conditions. The synthesis of high-symmetry complexes in high purity with significant lifetimes in solution and solid-state are essential for determining the role of ligand-field splitting, multiconfigurational behavior, and covalency in governing the reactivity and physical properties of these potentially technologically transformative tetravalent ions. We report the synthesis and physical characterization of an <i>S</i><sub>4</sub> symmetric, four-coordinate tetravalent terbium complex, [Tb(NP(1,2-bis-<i><sup>t</sup></i>Bu-diamidoethane)(NEt<sub>2</sub>))<sub>4</sub>] (where Et is ethyl and <i>t</i>Bu is <i>tert</i>-butyl). The ligand field in this complex is weak and the metal-ligand bonds sufficiently covalent so that the tetravalent terbium ion is stable and accessible via a mild oxidant from the anionic, trivalent, terbium precursor, [(Et<sub>2</sub>O)K][Tb(NP(1,2-bis-<i><sup>t</sup></i>Bu-diamidoethane)(NEt<sub>2</sub>))<sub>4</sub>]. The significant stability of the tetravalent complex enables its thorough characterization. The step-wise development of the supporting ligand points to key ligand control elements for further extending the known tetravalent lanthanide ions in molecular complexes. Magnetic susceptibility, electron paramagnetic resonance (EPR) spectroscopy, X-ray absorption near-edge spectroscopy (XAS), and density functional theory studies indicate a <i>4f<sup>7</sup></i> ground state for [Tb(NP(1,2-bis-<i><sup>t</sup></i>Bu-diamidoethane)(NEt<sub>2</sub>))<sub>4</sub>] with considerable zero-field splitting: demonstrating that magnetic, tetravalent lanthanide ions engage in covalent metal-ligand bonds. This result has significant implications for the use of tetravalent lanthanide ions in magnetic applications since the observed zero-field splitting is intermediate between that observed for the trivalent lanthanides and for the transition metals. The similarity of the multiconfigurational behavior in the ground state of [Tb(NP(1,2-bis-<i><sup>t</sup></i>Bu-diamidoethane)(NEt<sub>2</sub>))<sub>4</sub>] (measured by Tb L<sub>3</sub>-edge XAS) to that observed in TbO<sub>2</sub> implicates ligand control of multiconfigurational behavior as a key component of the stability of the complex.

Synthesis, Characterisation and Spectral Studies of some Molecular Adducts of Organotin(IV) Chlorides with Free Base Meso-Tetraarylporphyrins

2002 ◽  
Vol 2002 (12) ◽  
pp. 611-613 ◽  
Author(s):  
Mozaffar Asadi ◽  
Abedien Zabardasti
Keyword(s):  
General Formula ◽  
Molecular Complexes ◽  
Spectral Studies ◽  
Free Base ◽  
H Nmr ◽  
Elemental Microanalysis ◽  
Molecular Adducts

Some molecular complexes of diethyltin(IV) dichloride and methyltin(IV) trichloride with para-substituted meso-tetraphenylporphyrins of the general formula [(Et2SnCl2)2H2T(4-X)PP] and [(MeSnCl3)2H2T(4-X)PP]; {X= OCH3, CH3, H, and Cl} have been synthesised and characterised by means of 1H NMR, UV-Vis, and elemental microanalysis methods.

Coordination compounds containing 2-pyridylselenium ligands: synthesis, structural characterization, and antibacterial evaluation

2021 ◽  
Author(s):  
Rodrigo Cervo ◽  
Thaísa Regina Rocha Lopes ◽  
Adriana Righi de Vasconcelos ◽  
Juliana Felipetto Cargnelutti ◽  
Ricardo F. Schumacher ◽  
...  
Keyword(s):  
General Formula ◽  
Structural Characterization ◽  
Coordination Compounds ◽  
Molecular Complexes ◽  
Antibacterial Evaluation

Reactions between 3-amine-2-((pyridin-2-ylmethyl)selanyl)pyridine (L) and MX2 (M = Co, Cu, Zn; X = Cl, Br) result in the formation of the metal(II) molecular complexes 1–5 with the general formula [MX2(L)]....

Probing massive cold cores discovered by ISO in quiescent galactic molecular complexes

2002 ◽  
Vol 4 ◽  
pp. 133-133
Author(s):  
D. Teyssier ◽  
P. Hennebelle ◽  
M. Pérault
Keyword(s):  
Molecular Complexes

Dipole moments and molecular complexes

1964 ◽  
Vol 61 ◽  
pp. 125-131 ◽  
Author(s):  
J. W. Smith
Keyword(s):  
Dipole Moments ◽  
Molecular Complexes

X-ray Structure Refinement and Vibrational Spectroscopy of Ca8Gd2 (PO4)6 O2

2013 ◽  
Vol 12 (10) ◽  
pp. 719-726
Author(s):  
R. Ayadi ◽  
Mohamed Boujelbene ◽  
T. Mhiri
Keyword(s):  
Solid State ◽  
General Formula ◽  
Vibrational Spectroscopy ◽  
Powder Diffraction ◽  
Infrared Spectra ◽  
Solid State Reaction ◽  
Structure Refinement ◽  
Unit Cell ◽  
Cell Group ◽  
X Ray

The present paper is interested in the study of compounds from the apatite family with the general formula Ca10 (PO4)6A2. It particularly brings to light the exploitation of the distinctive stereochemistries of two Ca positions in apatite. In fact, Gd-Bearing oxyapatiteCa8 Gd2 (PO4)6O2 has been synthesized by solid state reaction and characterized by X-ray powder diffraction. The site occupancies of substituents is0.3333 in Gd and 0.3333 for Ca in the Ca(1) position and 0. 5 for Gd in the Ca (2) position.  Besides, the observed frequencies in the Raman and infrared spectra were explained and discussed on the basis of unit-cell group analyses.

Hydrothermal Synthesis and Solid-State Laser Refrigeration of Ytterbium-Doped Potassium Lutetium Fluoride (KLF) Microcrystals

2020 ◽  
Author(s):  
Xiaojing Xia ◽  
Anupum Pant ◽  
Xuezhe Zhou ◽  
Elena Dobretsova ◽  
Alex Bard ◽  
...  
Keyword(s):  
Hydrothermal Synthesis ◽  
Solid State ◽  
Information Science ◽  
Point Group ◽  
Solid State Laser ◽  
Lanthanide Ions ◽  
Group Symmetry ◽  
Luminescence Spectra ◽  
Crystalline Phases ◽  
State Laser

Fluoride crystals, due to their low phonon energies, are attractive hosts of trivalent lanthanide ions for applications in upconverting phosphors, quantum information science, and solid-state laser refrigeration. In this article, we report the rapid, low-cost hydrothermal synthesis of potassium lutetium fluoride (KLF) microcrystals for applications in solid-state laser refrigeration. Four crystalline phases were synthesized, namely orthorhombic K<sub>2</sub>LuF<sub>5</sub> (Pnma), trigonal KLuF<sub>4</sub> (P3<sub>1</sub>21), orthorhombic KLu<sub>2</sub>F<sub>7</sub> (Pna2<sub>1</sub>), and cubic KLu<sub>3</sub>F<sub>10</sub> (Fm3m), with each phase exhibiting unique microcrystalline morphologies. Luminescence spectra and emission lifetimes of the four crystalline phases were characterized based on the point-group symmetry of trivalent cations. Laser refrigeration was measured by observing both the optomechanical eigenfrequencies of microcrystals on cantilevers in vacuum, and also the Brownian dynamics of optically trapped microcrystals in water. Among all four crystalline phases, the most significant cooling was observed for 10%Yb:KLuF<sub>4</sub> with cooling of 8.6 $\pm$ 2.1 K below room temperature. Reduced heating was observed with 10%Yb:K<sub>2</sub>LuF<sub>5</sub>

Bond-length distributions for ions bonded to oxygen: Results for the lanthanides and actinides and discussion of the f-block contraction

2017 ◽  
Author(s):  
Olivier Charles Gagné
Keyword(s):  
Bond Length ◽  
Coordination Number ◽  
Lanthanide Ions ◽  
Lanthanide Contraction ◽  
Trivalent Lanthanide ◽  
Actinide Ions

Bond-length distributions have been examined for eighty-four configurations of the lanthanide ions and twenty-two configurations of the actinide ions bonded to oxygen. The lanthanide contraction for the trivalent lanthanide ions bonded to O<sup>2-</sup> is shown to vary as a function of coordination number and to diminish in scale with increasing coordination number.

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