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Synthesis, Crystal Structure, and Photophysical Properties of Novel (Monophthalocyaninato)lanthanide Complexes Stabilized by an Organometallic Tripodal Ligand
Author(s) -
Ke Hanzhong,
Wong WaiKwok,
Wong WaiYeung,
Tam HoiLam,
Poon ChunTing,
Jiang Fenglei
Publication year - 2009
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.200801125
Subject(s) - chemistry , lanthanide , phosphorescence , ligand (biochemistry) , cyclopentadienyl complex , crystallography , intramolecular force , crystal structure , tripodal ligand , metal , photochemistry , singlet state , phthalocyanine , terbium , ion , stereochemistry , excited state , fluorescence , catalysis , organic chemistry , physics , biochemistry , receptor , quantum mechanics , nuclear physics
An unprecedented series of (monophthalocyaninato)lanthanide(III) complexes {[PcYb(L OMe )] ( 3 ) and [( t Bu) 4 PcLn(L OMe )] [Ln = Yb ( 4 ), Er ( 5 )]} {Pc = phthalocyaninate, L OMe – = [(cyclopentadienyl)tris(dimethylphosphito)cobaltate(III)]} were prepared by the reaction of Ln[N(SiMe 3 ) 2 ] 3 · [LiCl(THF) 3 ] x (Ln = Yb or Er) with the corresponding phthalocyanine [H 2 Pc and H 2 ( t Bu) 4 Pc] followed by Na(L OMe ). X‐ray structural analysis of 3 reveals that the Yb 3+ ion is seven‐coordinate, surrounded by four nitrogen atoms from the phthalocyaninate dianion and three oxygen atoms from the anionic tripodal L OMe – ligand. The photophysical properties of these new mixed‐metal (monophthalocyaninato)lanthanide complexes are investigated. An efficient intramolecular energy transfer from ligand‐centered states to the metal ion manifold or metal‐centered states takes place for the Er 3+ complex, but there is a significant back‐energy transfer for the Yb 3+ complex. Singlet oxygen ( 1 O 2 ) phosphorescence was detected instead of the Yb 3+ emission in the photoluminescence spectra of 3 and 4 in the NIR region, but only the Er 3+ ion emission was observed for 5 . (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)