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Triphenylarsane Oxide Complexes of Lanthanide Nitrates: Polymorphs and Photophysics
Author(s) -
Barnes Francis H.,
Nicholas Aaron D.,
Melzer Henry,
Cormier Kaleb P.,
Kessler Matthew D.,
Patterson Howard H.,
Pike Robert D.
Publication year - 2019
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.201900137
Subject(s) - lanthanide , solvent , chemistry , luminescence , chloroform , crystallization , acetone , crystallography , ether , density functional theory , oxide , inorganic chemistry , materials science , organic chemistry , computational chemistry , ion , optoelectronics
trans ‐[ Ln (NO 3 ) 2 (Ph 3 AsO) 4 ](NO 3 ) 2 ( 1 ) and mer ‐[ Ln (NO 3 ) 3 (Ph 3 AsO) 3 ] ( 2 ) complexes were prepared from Ln (NO 3 ) 3 · x H 2 O and Ph 3 AsO in chloroform ( Ln = Y, Sm, Eu, Tb, and Dy). Production of complexes 1 vs. 2 and solvent content was found to be highly dependent on crystallization solvent choice. Tb and Eu produced only 1 , while the other Ln metals produced both 1 and 2 . Solvent‐free, acetone‐, and methanol‐containing polymorph series were identified for complexes 1 . Acetone/ether‐ and CH 2 Cl 2 ‐containing polymorph series were identified for complexes 2 . Luminescence measurements were performed on solvent‐free 1 ( Ln = Y, Eu, Tb, and Dy) and 2 ( Ln = Sm) at 78 K. Sensitized lanthanide emission bands via resonance energy transfer were observed in all cases, except the control ( Ln = Y). The efficiency of this energy transfer process varies amongst the lanthanide metals studied and was rationalized using Latva's empirical rule and Density Functional Theory calculations.