Wydział Chemii

Paula Gawryszewska

O. V. Moroz

Victor A. Trush

Vladimir M. Amirkhanov

Tadeusz Lis

Marcin Sobczyk

Miłosz Siczek

2012

ChemPlusChem

77

482-496

10.1002/cplu.201200026

Naukowa

Angielski

Artykuł

Lanthanide complexes with sulfonylamidophosphate‐type ligands: dibenzyl(phenylsulfonyl)amidophosphate (HSB) and di(4‐methylphenyl)‐phenylsulfonyl‐amidophosphate (HSK) have been synthesized and show promise as new sensitizers of visible and near‐infrared luminescence. They constitute a new part of coordination chemistry for this type of ligand, creating simultaneously a new class of lanthanide complexes with π‐conjugated ligands possessing the structural fragment SO₂NHP(O). Two series of stable lanthanide complexes Na[Ln(SB)₄] (1Ln) and Na[Ln(SK)₄] (2Ln), where Ln=Nd^III, Eu^III, Gd^III, Tb^III, Er^III, Yb^III, were characterized by X‐ray structure analysis. The IR, absorption, emission, and excitation spectra at 293, 77, and 4 K, as well as luminescence decay times and emission quantum yields were used to characterize the complexes in the solid state. The relation between the crystal structure and its spectroscopic properties is also discussed. The influence of the π–π stacking interactions and a ligand‐to‐metal charge transfer state on ligand‐to‐metal energy transfer efficiency was demonstrated and discussed. Crystal‐field lines determined from absorption and fluorescence spectra of 2Nd were used in computational analysis employing free‐ion operators, one‐electron crystal‐field operators, and two‐particle correlation crystal‐field operators. The performed analysis enabled the determination of the Hamiltonian parameters and an unambiguous assignment of 85 crystal‐field levels of Nd^III ion with a mean error of 12.0 cm⁻¹.

Crystal field, parameters, lanthanides, luminescence, π-πstacking interactions, sulphonylamidophosphates, X-ray diffraction

https://doi.org/10.1002/cplu.201200026

onlinelibrary.wiley.com