Cyclam-based dendrimers as ligands for lanthanide ions

Dalton Transactions : an International Journal of Inorganic Chemistry
Christophe SaudanFritz Vögtle

Abstract

We have investigated the complexation of lanthanide ions (Nd3+, Eu3+, Gd3+, Tb3+, Dy3+) with three cyclam-based ligands (cyclam = 1,4,8,11-tetraazacyclotetradecane), namely 1,4,8,11-tetrakis(naphthylmethyl)cyclam (1), and two dendrimers consisting of a cyclam core appended with four dimethoxybenzene and eight naphthyl units (2) and twelve dimethoxybenzene and sixteen naphthyl units (3). In the free ligands the fluorescence of the naphthyl units is strongly quenched by exciplex formation with the cyclam nitrogens. Complexation with the metal ions prevents exciplex formation and revives the intense naphthyl fluorescence. Fluorescence and NMR titration experiments have revealed the formation of complexes with different metal/ligand stoichiometries in the case of 1, 2 and 3. Surprisingly, the large dendrimer 3 gives rise to a stable [M(3)3]3+ species. Energy transfer from the lowest singlet and triplet excited states of the peripheral naphthyl units to the lower lying excited states of Nd3+, Eu3+, Tb3+, Dy3+ coordinated to the cyclam core does not take place.

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Citations

Jun 22, 2005·Chemical Communications : Chem Comm·Thorfinnur Gunnlaugsson, Joseph P Leonard
Jul 26, 2005·Analytical Sciences : the International Journal of the Japan Society for Analytical Chemistry·Jun KawakamiHaruo Kitahara
Jun 28, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Bing LiPengfei Yan
Jul 17, 2008·Dalton Transactions : an International Journal of Inorganic Chemistry·Sally E Plush, Thorfinnur Gunnlaugsson
Jun 12, 2010·Chemistry, an Asian Journal·Giacomo BergaminiFritz Vögtle
Dec 25, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Barbara BranchiFrank-Gerrit Klärner
Jan 25, 2013·Chemistry, an Asian Journal·Zeena S PillaiGiacomo Bergamini
Aug 5, 2009·Chemical Reviews·Koen Binnemans
Jan 12, 2010·The Journal of Physical Chemistry. B·Jukka AumanenJouko Korppi-Tommola
Nov 3, 2006·Organic Letters·Adam J PrestonJon R Parquette

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