The Solution Structure of Rhombic Lanthanide Complexes Analyzed with a Model-Free and Crystal-Field Independent Paramagnetic NMR Method:  Application to Nonaxial Trimetallic Complexes [LnxLu3-x(TACI-3H)2(H2O)6]3+(x= 1−3)

2004 ◽  
Vol 43 (4) ◽  
pp. 1517-1529 ◽  
Author(s):  
Nadjet Ouali ◽  
Jean-Pierre Rivera ◽  
David Chapon ◽  
Pascale Delangle ◽  
Claude Piguet
Keyword(s):  
Crystal Field ◽  
Lanthanide Complexes ◽  
Solution Structure ◽  
Paramagnetic Nmr ◽  
Nmr Method ◽  
Model Free ◽  
Field Independent

Solution structure and structural rearrangement in chiral dimeric ytterbium(iii) complexes determined by paramagnetic NMR and NIR-CD

2019 ◽  
Vol 48 (3) ◽  
pp. 882-890 ◽  
Author(s):  
Moreno Lelli ◽  
Lorenzo Di Bari
Keyword(s):  
Lanthanide Complexes ◽  
Solution Structure ◽  
Accurate Determination ◽  
Structural Rearrangement ◽  
Paramagnetic Nmr ◽  
Enantioselective Catalysis ◽  
Crucial Importance ◽  
Optical And Magnetic Properties ◽  
Structure In Solution

The accurate determination of the structure in solution of chiral lanthanide complexes is of crucial importance to understand enantioselective catalysis, and the optical and magnetic properties.

Pseudocontact shifts in lanthanide complexes with variable crystal field parameters

2011 ◽  
Vol 255 (23-24) ◽  
pp. 2810-2820 ◽  
Author(s):  
Sebastiano Di Pietro ◽  
Samuele Lo Piano ◽  
Lorenzo Di Bari
Keyword(s):  
Crystal Field ◽  
Lanthanide Complexes ◽  
Pseudocontact Shifts ◽  
Crystal Field Parameters

The crystal-field-independent transitions in orthoaxial mniicomplexes.

1973 ◽  
Vol 19 ◽  
pp. 709-717 ◽  
Author(s):  
Jacek Karwowoski ◽  
Alicja Lodzinska
Keyword(s):  
Crystal Field ◽  
Field Independent

scholarly journals Using Remote Substituents to Control Solution Structure and Anion Binding in Lanthanide Complexes

2013 ◽  
Vol 19 (49) ◽  
pp. 16566-16571 ◽  
Author(s):  
Manuel Tropiano ◽  
Octavia A. Blackburn ◽  
James A. Tilney ◽  
Leila R. Hill ◽  
Matteo P. Placidi ◽  
...  
Keyword(s):  
Lanthanide Complexes ◽  
Solution Structure ◽  
Anion Binding ◽  
Control Solution

scholarly journals Ab Initio Non-Covalent Crystal Field Theory for Lanthanide Complexes: A Multiconfigurational Non-Orthogonal Group Functions Approach

2020 ◽  
Author(s):  
Alessandro Soncini ◽  
MATTEO PICCARDO
Keyword(s):  
Magnetic Properties ◽  
Perturbation Theory ◽  
Ab Initio ◽  
Crystal Field ◽  
Orthogonal Group ◽  
Lanthanide Complexes ◽  
Field Energy ◽  
First Order ◽  
Group Functions ◽  
Metal Ligand

We present a non-orthogonal fragment ab initio methodology for the calculation of crystal field energy levels and magnetic properties in lanthanide complexes, implementing a systematic description of non-covalent contributions to metal-ligand bonding. The approach has two steps. In the first step, appropriate ab initio wavefunctions for the various ionic fragments (lanthanide ion and coordinating ligands) are separately optimized, accounting for the electrostatic influence of the surrounding environment, within various approximations. In the second and final step, the scalar relativistic (DKH2) electrostatic Hamiltonian of the whole molecule is represented on the basis of the optimized metal-ligand multiconfigurational non-orthogonal group functions (MC-NOGF), and reduced to an effective (2J+1)-dimensional non-orthogonal Configuration Interaction (CI) problem via L{\"o}wdin-partitioning. Within the proposed formalism, the projected Hamiltonian can be implemented to any desired order of perturbation theory in the fragment-localised excitations out of the degenerate space, and its eigenvalues and eigenfunctions are systematic approximations to the crystal field energies and wavefunctions. We present a preliminary implementation of the proposed MC-NOGF method to first-order degenerate perturbation theory within our own ab initio code CERES, and compare its performance both with the simpler non-covalent orthogonal ab initio approach Fragment Ab Initio Model Potential (FAIMP) approximation, and with the full CAHF/CASCI-SO method, accounting for metal-ligand covalency in a mean-field manner. We find that energies and magnetic properties for 44 complexes obtained via an iteratively optimized version of our MC-NOGF first-order non-covalent method, compare remarkably well to the full CAHF/CASCI-SO method including metal-ligand covalency, and are superior to the best purely electrostatic results achieved via an iteratively optimized version of the FAIMP approach.<br>

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