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Superchiral Pd 3 L 6 Coordination Complex and Its Reversible Structural Conversion into Pd 3 L 3 Cl 6 Metallocycles
Author(s) -
Jurček Ondřej,
Bonakdarzadeh Pia,
Kalenius Elina,
Linnanto Juha Matti,
Groessl Michael,
Knochenmuss Richard,
Ihalainen Janne A.,
Rissanen Kari
Publication year - 2015
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201506539
Subject(s) - trimer , chemistry , cationic polymerization , dimer , ligand (biochemistry) , enantiomer , supramolecular chemistry , crystallography , circular dichroism , coordination complex , porphyrin , stereochemistry , metal , crystal structure , photochemistry , organic chemistry , biochemistry , receptor
Large, non‐symmetrical, inherently chiral bispyridyl ligand L derived from natural ursodeoxycholic bile acid was used for square–planar coordination of tetravalent Pd II , yielding the cationic single enantiomer of superchiral coordination complex 1 Pd 3 L 6 containing 60 well‐defined chiral centers in its flower‐like structure. Complex 1 can readily be transformed by addition of chloride into a smaller enantiomerically pure cyclic trimer 2 Pd 3 L 3 Cl 6 containing 30 chiral centers. This transformation is reversible and can be restored by the addition of silver cations. Furthermore, a mixture of two constitutional isomers of trimer, 2 and 2′ , and dimer, 3 and 3′ , can be obtained directly from L by its coordination to trans‐ or cis‐N ‐pyridyl‐coordinating Pd II . These intriguing, water‐resistant, stable supramolecular assemblies have been thoroughly described by 1 H DOSY NMR, mass spectrometry, circular dichroism, molecular modelling, and drift tube ion‐mobility mass spectrometry.