Correlation of the structural information obtained for europium-chelate ensembles from gas-phase photoluminescence and ion-mobility spectroscopy with density-functional computations and ligand-field theory

Abstract

We report a combined investigation of europium(iii)9-oxo-phenalen-1-one (PLN) coordination complexes, [Eu(PLN)AE] with AE = Mg, Ca, and Sr, using gas-phase photoluminescence, trapped ion-mobility spectrometry and density-functional computations. In order to sort out the structural impact of the alkali earth dications on the photoluminescence spectra, the experimental data are compared to the predicted ligand-field splittings as well as to the collision cross-sections for different isomers of [Eu(PLN)AE]. The best fitting interpretation is that one isomer family predominantly contributes to the recorded luminescence. The present work demonstrates the complexity of the coordination patterns of multicenter lanthanoid chelates involved in dynamical equilibria and the pertinence of using isolation techniques to elucidate their photophysical properties.

Aminocatalyzed Synthesis of Enantioenriched Phenalene Skeletons through a Friedel–Crafts/Cyclization Strategy

“…The electronic and molecular features of phenalene derivatives have been harnessed in a range of contexts. For instance, 9-hydroxyphenalenone compounds 2 have been successfully used as ligands in coordination chemistry due to their propensity to form chelates with several metal ions . In addition, phenalene derivatives are interesting building blocks for the preparation of stable π-conjugated cations and radicals with potential applications in photochemistry and materials science .…”

Detection of Intermediates in Dual Gold Catalysis Using High-Resolution Ion Mobility Mass Spectrometry

“…Identical separations were obtained on the two setups. As described in our study of coordination complexes, the experimental mobilities K = ν g / E = A /( U release – U out ) of ions sequentially released from the TIMS cell after trapping depend on the corresponding trapping electric field window E ± Δ E and the velocity of the carrier gas v g . This is more conveniently expressed by a single calibration constant A , the release voltage U release , and the voltage U out applied to the tunnel exit.…”

Vibronic Coupling Analysis of the Ligand-Centered Phosphorescence of Gas-Phase Gd(III) and Lu(III) 9-Oxophenalen-1-one Complexes

“…[Ln­(PLN) 2 ] + cations with Ln = Gd 3+ and Lu 3+ result from the decomposition of complexes with higher coordination numbers such as [Ln­(PLN) 4 Na] or [Ln 9 (PLN) 16 (OH) 10 ]Cl in coordinating solvents such as DMSO and alcohols. Their synthesis was reported in previous publications. − Isolated [Ln­(PLN) 2 ] + species are obtained by electrospray ionization from solution.…”