UNIGE document Scientific Article
previous document  unige:3572  next document
add to browser collection
Title

Towards inert and pre-organized d-block-containing receptors for trivalent lanthanides: The synthesis and characterization of triple-helical monometallic OsII and bimetallic OsII-LnIII complexes

Authors
Published in Dalton Transactions. 2008, vol. 28, no. 26, p. 3661-3677
Abstract The mononuclear OsII complex [Os( L1)3](PF6)2 ( L1 = 5-methyl(1-methylbenzimidazol-2-yl)pyridine) is an obvious candidate for the design of an inert d-block-based tripodal receptor capable of binding and photosensitizing trivalent lanthanides (LnIII). It has thus been prepared and its two enantiomeric meridional (-mer and -mer) and facial (rac-fac) isomers have been separated by ion-exchange chromatography. The optical isomers have been characterized by CD spectroscopy and assignments of absolute configuration confirmed by an X-ray crystallographic study of -mer-[Os( L1)3](PF6)2·1.5MeCN (monoclinic, P21, Z = 4). Comparison of the latter structure with that of racemic fac-[Os( L1)3](PF6)2 (monoclinic, C2/c, Z = 8) and [Os(bipy)3](PF6)2 (where bipy = 2,2-bipyridine) shows minimal structural variations, but differences are observed in the photophysical and electrochemical properties of the respective compounds. Luminescence emissions from OsII complexes of L1 are typically lower in energy, with shorter lifetimes and lower quantum yields than their bipy analogues, whilst metal-centred oxidation processes are more facile due to the enhanced -donor ability of L1. The key relationships between these parameters are discussed. Finally, though challenged by (i) the low reactivity of many osmium precursors and (ii) the irreversible formation of competing side products, the synthesis and purification of the heterobimetallic triple-stranded helicate HHH-[OsLu( L2)3](CF3SO3)5 has been realised, in which L2 is a segmental ligand containing the same bidentate unit as that found in L1 further connected to a tridentate binding site adapted for complexing LnIII. Its solid-state structure has been established by X-ray crystallography (triclinic, P, Z = 2).
Identifiers
Full text
Structures
Research group Groupe Hauser
Citation
(ISO format)
RIIS-JOHANNESSEN, Thomas et al. Towards inert and pre-organized d-block-containing receptors for trivalent lanthanides: The synthesis and characterization of triple-helical monometallic OsII and bimetallic OsII-LnIII complexes. In: Dalton Transactions, 2008, vol. 28, n° 26, p. 3661-3677. https://archive-ouverte.unige.ch/unige:3572

265 hits

201 downloads

Update

Deposited on : 2009-10-02

Export document
Format :
Citation style :