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Anion‐Induced Assembly of Hexacoordinate Rare‐Earth(III) Complexes
Author(s) -
Tanase Stefania,
Sottini Silvia,
Marvaud Valerie,
Groenen Edgar J. J.,
Chamoreau LiseMarie
Publication year - 2010
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201000059
Subject(s) - hexacoordinate , chemistry , ligand (biochemistry) , deprotonation , crystallography , intramolecular force , crystal structure , molecule , lanthanide , luminescence , stereochemistry , ion , organic chemistry , biochemistry , physics , receptor , optoelectronics , silicon
Rare‐earth(III) complexes of the general formula [RE{(Hsal) 3 tren} 2 ](CF 3 SO 3 ) 3 · n CH 3 CN, where RE is Eu ( 1 ), Gd ( 2 ), and Tb ( 3 ), and (Hsal) 3 tren is tris[2‐(salicylideneimino)ethyl]amine, have been synthesized and structurally characterized. X‐ray crystallographic studies show that the rare‐earth(III) center is coordinated by six oxygen atoms that belong to thephenolato groups of two (Hsal) 3 tren ligand molecules to give an unusual hexacoordinate geometry. The molecular structure is stabilized by strong intramolecular interactions established between the hydrogen atoms located on the three imino nitrogen atoms and the deprotonated phenol oxygen atoms of each ligand. Luminescence studies have indicated the presence of efficient nonradiative deactivation pathways in 1 – 3 , and only a weak ligand emission was observed ( λ exc = 275 nm, λ em = 545 nm) in all cases. Temperature‐dependent magnetic susceptibility studies have shown that crystal field effects are dominant for complex 3 , whilst small antiferromagnetic interactions have been observed in 2 .