Synthesis, Structures, and Luminescent Properties of Lanthanide Complexes with Triphenylphospine Oxide

Abstract

Seven lanthanide complexes [Ln(OPPh 3 ) 3 (NO 3 ) 3 ] (1-3) (OPPh 3 = triphenylphosphine oxide, Ln = Nd, Sm, Gd), [Dy(OPPh 3 ) 4 (NO 3 ) 2 ](NO 3 ) (4), [Ln(OPPh 3 ) 3 (NO 3 ) 3 ] 2 (5-7) (Ln = Pr, Eu, Gd) were synthesized by the reactions of different lanthanide salts and OPPh 3 ligand in the air. These complexes were characterized by single-crystal X-ray diffraction analysis, elemental analysis, IR and fluorescence spectra. Structure analysis shows that complexes 1-4 are mononuclear complexes formed by OPPh 3 ligands and nitrates. The

Triphenylphosphane Oxide Complexes of Lanthanide Nitrates: Polymorphs and Photophysics

“…While the Yb cation was fully ordered, the anion showed significant positional disorder for all four nitrate ions and two of the three phenyl groups. The trans ‐[ Ln (NO 3 ) 2 (Ph 3 PO) 4 ] + cation arrangement (treating the nitrate ions as single ligands) is known, having been reported for Ln = Dy and Lu , . The anion, on the other hand, represents a new Ln coordination environment.…”

“…The identifiable polymorphic groups for this series, both those with and without solvent present, are distinguished in Table . The current solvent‐free structures fill out a series of monoclinic isomorphs (polymorph series 1 , P 2 1 / c, a = 11.1 Å, b = 11.4 Å, c = 41.7 Å, β = 92.5°) that was previously recognized only for Ln = Y and Gd , . In addition to re‐determining the Gd structure, we have added to series 1 the Ln = Sm, Eu, Tb, Dy, and Er isomorphs.…”

“…The isomorphic series, 2 , is also monoclinic ( P 2 1 / c, a = 14.6 Å, b = 18.4 Å, c = 20.6 Å, β = 102°). Prior to this work, two examples of 2 had been reported, Ln (NO 3 ) 3 (Ph 3 PO) 3 ( Ln = Nd and Sm) , . Neither of these complexes were reported as solvates, having been crystallized from ethanol.…”

“…Thus, polymorph 2 appears to be able to admit a small amount of solvent without disruption of its structure. Polymorph 3 (orthorhombic Pbca, a = 25.4 Å, b = 24.0 Å, c = 35.0 Å) has only recently been reported, being noted for Pr, Eu, and Gd . It features two independent molecules in the crystallographic repeat unit.…”

“…Numerous solvent‐free Ln (NO 3 ) 3 (Ph 3 PO) 3 complexes have also been structurally characterized for Ln = Y, La, Pr, Nd, Sm, Gd, and Eu , , , . Polymorphism is clearly an important factor in these series of complexes, given the fact that two polymorphs each have been identified for Nd(NO 3 ) 3 (Ph 3 PO) 3 ,, and Gd(NO 3 ) 3 (Ph 3 PO) 3 . In this article, we report on the synthesis, new crystal structures, polymorphism, and luminescence utilizing the antenna effect for these complexes.…”