ORGANIC
LETTERS
2002
Vol. 4, No. 14
2289-2292
Ring-in-Ring Structures from
Phenanthroline Macrocycles with Exo-
and Endotopic Binding Sites
,†
Michael Schmittel,* Andrea Ganz,‡ and Dieter Fenske§
FB8-OC1 (Chemie-Biologie), UniVersita¨t Siegen, Adolf-Reichwein-Str.,
D-57068 Siegen, Germany, Institut fu¨r Organische Chemie, UniVersita¨t Wu¨rzburg,
Am Hubland, D-97074 Wu¨rzburg, Germany, and Institut fu¨r Anorganische Chemie,
UniVersita¨t Karlsruhe, Engesserstr. 3045, D-76128 Karlsruhe, Germany
Received March 18, 2002
ABSTRACT
Three metallosupramolecular ring-in-ring structures are assembled using the HETPHEN concept (in the presence of copper(I)) with macrocyclic
phenanthrolines exhibiting exotopic and endotopic coordination sites.
The seminal work by Sauvage in 19831 on the high-yield
formation of catenanes via the intermediate formation of
catenates has moved phenanthrolines and bipyridines into
the focus of metallosupramolecular chemistry.2 By using the
templating effect of tetrahedrally coordinating metal ions,
mostly copper(I) and silver(I), many additional challenging
structures, such pseudorotaxanes,3 grids,4 double/triple he-
licates,5 knots,6 and huge wheels,7 were realized by several
groups in the ensuing years. Many of those structures contain
as a key element heteroleptic complexes [M(diim1)(diim2)]n+
(diim ) diimines, such as phenanthrolines, bipyridines)
whose formation is guided by the principles of maximum
site occupancy and cooperativity but interestingly not by
independent, well-directed tactics.
A while ago, we developed the HETPHEN concept, which
allows the preparation of heteroleptic bisphenanthroline or
bisbipyridine copper(I)8 and silver(I)9 complexes. It occurred
to us that the enforced formation of heteroleptic diimine
complexes should allow access to structural motifs that on
† Universita¨t Siegen.
‡ Universita¨t Wu¨rzburg.
§ Universita¨t Karlsruhe.
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10.1021/ol025885t CCC: $22.00 © 2002 American Chemical Society
Published on Web 06/11/2002