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A Cyclam Core Dendrimer Containing Dansyl and Oligoethylene Glycol Chains in the Branches: Protonation and Metal Coordination
Author(s) -
Branchi Barbara,
Ceroni Paola,
Bergamini Giacomo,
Balzani Vincenzo,
Maestri Mauro,
van Heyst Jeroen,
Lee SangKyu,
Luppertz Friedhelm,
Vögtle Fritz
Publication year - 2006
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200601129
Subject(s) - cyclam , protonation , chemistry , dendrimer , amine gas treating , amide , metal ions in aqueous solution , metal , photochemistry , medicinal chemistry , polymer chemistry , organic chemistry , ion
We have synthesized a dendrimer ( 1 ) consisting of a 1,4,8,11‐tetraazacyclotetradecane (cyclam) core, appended with four benzyl substituents that carry, in the 3‐ and 5‐positions, a dansyl amide derivative (of type 2 ), in which the amide hydrogen is replaced by a benzyl unit that carries an oligoethylene glycol chain in the 3‐ and 5‐positions. All together, the dendrimer contains 16 potentially luminescent moieties (eight dansyl‐ and eight dimethoxybenzene‐type units) and three distinct types of multivalent sites that, in principle, can be protonated or coordinated to metal ions (the cyclam nitrogen atoms, the amine moieties of the eight dansyl units, and the 16 oligoethylene glycol chains). We have studied the absorption and luminescence properties of 1 , 2 , and 3 in acetonitrile and the changes taking place upon titration with acid and a variety of divalent (Co 2+ , Ni 2+ , Cu 2+ , Zn 2+ ), and trivalent (Nd 3+ , Eu 3+ , Gd 3+ ) metal ions as triflate and/or nitrate salts. The results obtained show that: 1) double protonation of the cyclam ring takes place before protonation of the dansyl units; 2) the oligoethylene glycol chains do not interfere with protonation of the cyclam core and the dansyl units in the ground state, but affect the luminescence of the protonated dansyl units; 3) the first equivalent of metal ion is coordinated by the cyclam core; 4) the interaction of the resulting cyclam complex with the appended dansyl units depends on the nature of the metal ion; 5) coordination of metal ions by the dansyl units follows at high metal‐ion concentrations; 6) the effect of the metal ion depends on the nature of the counterion. This example demonstrates that dendrimers may exhibit complete functionality resulting from the integration of the specific properties of their component units.