Premium
Triphenylphosphane Oxide Complexes of Lanthanide Nitrates: Polymorphs and Photophysics
Author(s) -
Barnes Francis H.,
Kelly Andrew W.,
Melzer Henry,
Patterson Howard H.,
Pike Robert D.
Publication year - 2018
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201800096
Subject(s) - lanthanide , chemistry , luminescence , ion , ligand (biochemistry) , crystallography , chelation , oxidation state , inorganic chemistry , catalysis , materials science , biochemistry , receptor , optoelectronics , organic chemistry
A series of mer ‐[ Ln (NO 3 ) 3 (Ph 3 PO) 3 ] complexes were prepared from Ln (NO 3 ) 3 · x H 2 O and Ph 3 PO in chloroform ( Ln = La, Nd, Sm, Eu, Gd, Tb, Dy, and Er). The La and Nd complexes were 0.25 CHCl 3 solvates, whereas the others were solvent‐free. The identical reaction using Yb(NO 3 ) 3 · x H 2 O produced the unique salt trans ‐[Yb(NO 3 ) 2 (Ph 3 PO) 4 ][Yb(NO 3 ) 4 (Ph 3 PO)] · Et 2 O. All nitrate ions in all complexes are η 2 ‐chelating. A comparison of the various [ Ln (NO 3 ) 3 (Ph 3 PO) 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 (NO 3 ) 3 (Ph 3 PO) 3 ] ( Ln = Y, La, Nd, Sm, Eu, Gd, Tb, and Dy), trans ‐[Yb(NO 3 ) 2 (Ph 3 PO) 4 ][Yb(NO 3 ) 4 (Ph 3 PO)] and Ph 3 PO assignments are reported. Latva's empirical rule allows for the antenna effect, in which energy is transferred from the triplet state of the Ph 3 PO ligand, to occur only for Tb 3+ . Excitation via Ph 3 PO results in strong green luminescence for Tb 3+ having twice the intensity as that which results from direct excitation of the f‐f transitions.