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Fluoride Binding and Crystal‐Field Analysis of Lanthanide Complexes of Tetrapicolyl‐Appended Cyclen
Author(s) -
Blackburn Octavia A.,
Kenwright Alan M.,
Jupp Andrew R.,
Goicoechea Jose M.,
Beer Paul D.,
Faulkner Stephen
Publication year - 2016
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.201601170
Subject(s) - cyclen , lanthanide , fluoride , chemistry , crystallography , molecule , anisotropy , affinities , sign (mathematics) , crystal (programming language) , computational chemistry , inorganic chemistry , stereochemistry , ion , physics , organic chemistry , mathematics , mathematical analysis , quantum mechanics , computer science , programming language
Lanthanide complexes of tetrapicolyl cyclen displayed remarkably high affinities for fluoride (log K ≈5) in water, and were shown to form 1:1 complexes. The behaviour of these systems can be rationalised by changes to the magnitude of the crystal‐field parameter, B 20. However, such changes are not invariably accompanied by a change in sign of this parameter: for early lanthanides, the N8 donor set with a coordinated axial water molecule ensures that the magnetic anisotropy has the opposite sense to that observed in the analogous dehydrated lanthanide complexes.