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[1+1] Asymmetric Compartmental Macrocycles Bearing a Pendant Arm and Related s,f ‐Heterodinuclear Complexes Containing Lanthanide( III ) and Sodium Ions
Author(s) -
Tamburini Sergio,
Casellato Umberto,
Bertolo Laura,
Alessandro Vigato Pietro
Publication year - 2005
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200400955
Subject(s) - chemistry , lanthanide , crystallography , monoclinic crystal system , ligand (biochemistry) , pentagonal bipyramidal molecular geometry , sodium , crystal structure , ether , crown ether , stereochemistry , bipyramid , ion , inorganic chemistry , organic chemistry , biochemistry , receptor
[1+1] Asymmetric compartmental macrocycles and/or related mononuclear, homodinuclear and sodium( I )‐lanthanide( III ) heterodinuclear complexes are reported and their properties investigated by SEM‐EDS microscopy and 1 H, 13 C and 23 Na NMR spectroscopy. These ligands bear a pendant arm, represented by a ‐CH 2 COOH (H 3 L A ), ‐CH 2 C 5 H 4 N (H 2 L B ) or‐CH 2 C 6 H 4 OH (H 3 L C ) group bonded to the aminic nitrogen, and contain an O 2 O 3 crown‐ether‐like chamber and an N 3 XO 2 (where X = O, N) Schiff‐base chamber. It was found that the lanthanide( III ) ion resides in the N 3 XO 2 chamber while the sodium( I ) ion fills the O 2 O 3 crown‐ether‐like chamber, as ascertained for the complex [DyNa(L C )(PrOH)(Cl)] by a single‐crystal X‐ray structural investigation. The complex is monoclinic, space group P 2 1 / c , with a = 9.601(2), b = 12.927(2), c = 26.638(4) Å, β = 99.55(3)°. The dysprosium ion is seven‐coordinate in the N 3 O 2 site, showing a pentagonal‐bipyramid‐coordination polyhedron and bonded, in the axial positions, to a chlorine ion and to the oxygen of the pendant phenolic group of the ligand. The sodium ion is six‐coordinate in the O 3 O 2 site and bonded to the propyl alcohol oxygen. Furthermore, the potential use of these complexes as molecular probes for the selective recognition of specific metal ions has been tested. In particular, their ability to act as shift reagents towards Na + was investigated by 23 Na NMR spectroscopy. The relationship between the structure of these complexes in the solid state and in solution is reported. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)