Issue 22, 2006

Encapsulation of labile trivalent lanthanides into a homobimetallic chromium(iii)-containing triple-stranded helicate. Synthesis, characterization, and divergent intramolecular energy transfers

Abstract

The segmental bidentate–tridentate–bidentate ligand L2 reacts with MII (M = Cr, Zn) and LnIII (Ln = La, Eu, Gd, Tb, Lu) to give the heterotrimetallic triple-stranded helicates [MLnM(L2)3]7+. For M = ZnII, the isolated complexes [ZnLnZn(L2)3](CF3SO3)7 (Ln = Eu, Tb) display only lanthanide-centred luminescence arising from the pseudo-tricapped trigonal prismatic LnN9 coordination site. For M = CrII, rapid air oxidation provides CrIII and leads to the isolation of inert [CrLnCr(L2)3](CF3SO3)9 (Ln = Eu, Tb) complexes, in which divergent intramolecular Ln → Cr energy transfers can be evidenced. Taking [ZnEuZn(L2)3]7+ as a luminescent standard for Eu-centred emission, a quantitative treatment of the energy migration processes indicates that the rate constant characterizing the Eu → Cr energy transfer is more efficient in the trimetallic system, than in the analogous simple bimetallic edifice. Particular attention is focused on potential control of directional energy transfer processes in Cr–Ln pairs.

Graphical abstract: Encapsulation of labile trivalent lanthanides into a homobimetallic chromium(iii)-containing triple-stranded helicate. Synthesis, characterization, and divergent intramolecular energy transfers

Supplementary files

Article information

Article type
Paper
Submitted
17 Feb 2006
Accepted
20 Mar 2006
First published
04 Apr 2006

Dalton Trans., 2006, 2647-2660

Encapsulation of labile trivalent lanthanides into a homobimetallic chromium(III)-containing triple-stranded helicate. Synthesis, characterization, and divergent intramolecular energy transfers

M. Cantuel, F. Gumy, J. G. Bünzli and C. Piguet, Dalton Trans., 2006, 2647 DOI: 10.1039/B602392D

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