We are never ever getting (back to) ideal symmetry: structure and luminescence in a ten-coordinated europium(iii) sulfate crystal

Abstract

Our theoretical treatment of electronic structure in coordination complexes often rests on assumptions of symmetry. Experiments rarely provide fully symmetric systems to study. In solution, fluctuation in solvation, variations in...

Long story short: donor set symmetry in [Eu(DOTA)(H2O)]−crystals determines the electronic structure

“…Symmetry deviation analyses with AlignIt were performed on all crystal structures against an idealized model polyhedra. 33 The symmetry deviation value, σ ideal , was used to evaluate the average symmetry in the structures. In all cases, the average bond length in the three nine-coordinated Eu(DOTA)(H 2 O) polyhedra was used for scaling before the symmetry deviation values were calculated.…”

“…In all cases, the average bond length in the three nine-coordinated Eu(DOTA)(H 2 O) polyhedra was used for scaling before the symmetry deviation values were calculated. A complete introduction to AlignIt is available from Thomsen et al ., 33 and a guide to using the script in found in the ESI †…”

“…To relate the crystal structures of complexes from different compounds, a measure of the actual site symmetry must be used. We recently introduced the symmetry deviation value, σ ideal , 33,34 which compares coordination geometries between compounds and relates the coordination geometry to an idealised polyhedron. Here, we expand the σ ideal -value for use with nine-vertex coordination geometries.…”

Long Story Short: Donor Set Symmetry in Eu(DOTA) Crystals Determines the Electronic Structure

“…The symmetry deviation value, σideal, is computed using our AlignIt approach. 33,34 The method builds on the Continuous Symmetry Measure approach and its incorporation into the program SHAPE, [40][41][42][43][44][45][46][47][48] and was developed to compare the coordination geometry of ten-coordinated lanthanide complexes. The symmetry deviation value, σideal, is calculated using equation 1, following the detailed methodology described in the ESI.…”

“…To relate the crystal structures of complexes from different compounds, a measure of the actual site symmetry must be used. We recently introduced the symmetry deviation value, σideal, 33,34 that compares coordination geometries between compounds and relate the coordination geometry to idealised polyhedra. Here, we expand the σideal-value for use with nine-vertex coordination geometries.…”