Macrocyclic receptor exhibiting unprecedented selectivity for light lanthanides.
We report a new macrocyclic ligand, N,N'-bis[(6-carboxy-2-pyridil)methyl]-4,13-diaza-18-crown-6 (H(2)bp18c6), designed for complexation of lanthanide ions in aqueous solution. Potentiometric measurements evidence an unprecedented selectivity of bp18c6 for the large Ln(III) ions. Among the different Ln(III) ions, La(III) and Ce(III) show the highest log K(ML) values, with a dramatic drop of the stability observed from Ce(III) to Lu(III) as the ionic radius of the Ln(III) ions decreases (log K(CeL) - log K(LuL) = 6.9). The X-ray crystal structures of the Gd(III) and Yb(III) complexes show that the metal ion is directly bound to the 10 donor atoms of the bp18c6 ligand. The structure of the complexes in solution has been investigated by (1)H and (13)C NMR spectroscopy, as well as by theoretical calculations performed at the DFT (B3LYP) level. Our results indicate that a conformational change occurs around the middle of the lanthanide series: for the larger Ln(III) ions the most stable conformation is Delta(deltalambdadelta)(deltalambdadelta), while for the smallest Ln(III) ions (Gd-Lu) our calculations predict the Delta(lambdadeltalambda)(lambdadeltalambda) form being the most stable one. This structural change was confirmed by the analysis of the Ce(III)-, Pr(III)-, and Yb(III)-induced paramagnetic (1)H shifts. The selectivity that bp18c6 shows for the large Ln(III) ions can be attributed to a better fit between the light Ln(III) ions and the relatively large crown fragment of the ligand. Indeed, our DFT calculations indicate that the interaction between the Ln(III) ion and several donor atoms of the crown moiety is weakened as the ionic radius of the metal ion decreases.
Roca-Sabio
Adrián
A
Departamento de Química Fundamental, Universidade da Coruña, Campus da Zapateira, Spain.
Mato-Iglesias
Marta
M
Esteban-Gómez
David
D
Tóth
Eva
E
de Blas
Andrés
A
Platas-Iglesias
Carlos
C
Rodríguez-Blas
Teresa
T
D018360:Crystallography, X-Ray; D006863:Hydrogen-Ion Concentration; D028581:Lanthanoid Series Elements / Q000737:chemistry*; D008024:Ligands; D047028:Macrocyclic Compounds / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry
D028581:Lanthanoid Series Elements; D008024:Ligands; D047028:Macrocyclic Compounds; D009942:Organometallic Compounds