Triphenylphosphane Oxide Complexes of Lanthanide Nitrates: Polymorphs and Photophysics

A series of mer‐[Ln(NO3)3(Ph3PO)3] complexes were prepared from Ln(NO3)3·xH2O and Ph3PO in chloroform (Ln = La, Nd, Sm, Eu, Gd, Tb, Dy, and Er). The La and Nd complexes were 0.25 CHCl3 solvates, whereas the others were solvent‐free. The identical reaction using Yb(NO3)3·xH2O produced the unique salt...

Full description

Saved in:
Bibliographic Details
Published in:Zeitschrift für anorganische und allgemeine Chemie (1950) 2018-06, Vol.644 (11), p.525-533
Main Authors: Barnes, Francis H., Kelly, Andrew W., Melzer, Henry, Patterson, Howard H., Pike, Robert D.
Format: Article
Language:English
Subjects:
Antenna effect
Chelation
Chloroform
Dysprosium
Erbium
Excitation
Gadolinium
Lanthanides
Lanthanum
Luminescence
Nitrates
Samarium
Triphenylphosphane oxide
X‐ray crystal structure
Ytterbium
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:A series of mer‐[Ln(NO3)3(Ph3PO)3] complexes were prepared from Ln(NO3)3·xH2O and Ph3PO in chloroform (Ln = La, Nd, Sm, Eu, Gd, Tb, Dy, and Er). The La and Nd complexes were 0.25 CHCl3 solvates, whereas the others were solvent‐free. The identical reaction using Yb(NO3)3·xH2O produced the unique salt trans‐[Yb(NO3)2(Ph3PO)4][Yb(NO3)4(Ph3PO)]·Et2O. All nitrate ions in all complexes are η2‐chelating. A comparison of the various [Ln(NO3)3(Ph3PO)3] structures, including those in the literature, reveals at least four common polymorphs, each of which is represented by isomorphic structures of multiple Ln ions. Luminescence of mer‐[Ln(NO3)3(Ph3PO)3] (Ln = Y, La, Nd, Sm, Eu, Gd, Tb, and Dy), trans‐[Yb(NO3)2(Ph3PO)4][Yb(NO3)4(Ph3PO)] and Ph3PO assignments are reported. Latva's empirical rule allows for the antenna effect, in which energy is transferred from the triplet state of the Ph3PO ligand, to occur only for Tb3+. Excitation via Ph3PO results in strong green luminescence for Tb3+ having twice the intensity as that which results from direct excitation of the f‐f transitions.
ISSN:0044-2313
1521-3749
DOI:10.1002/zaac.201800096