Strongly Circularly Polarized Emission from Water-Soluble Eu(III)- and Tb(III)-Based Complexes: A Structural and Spectroscopic Study.
Inorg Chem
; 56(8): 4413-4422, 2017 Apr 17.
Article
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| ID: mdl-28388073
ABSTRACT
Water-soluble Eu(III) and Tb(III) complexes with N,N'-bis(2-pyridylmethyl)-trans-1,2-diaminocyclohexane-N,N'-diacetic acid (H2bpcd) have been synthesized and characterized in their racemic and enantiopure forms. The ligand has been designed to bind Ln(III) ions, providing a dissymmetric environment able to solicit strong chiroptical features while at the same time leaving a few coordination sites available for engaging further ancillary ligands. Potentiometric studies show that Ln(III) complexes have a relatively good stability and that at pH 7 the [Ln(bpcd)]+ species is largely dominant. DFT calculations carried out on the (S,S)-[Y(bpcd)(H2O)5]+ complexes (the closed-shell equivalents of [Eu(bpcd)(H2O)5]+ and [Tb(bpcd)(H2O)5]+) indicate that the two trans-O,O and trans-Npy,Npy configurations are equally stable in solution and present two coordinated water molecules. This is in agreement with the hydration number â¼2.6 determined by luminescence lifetime measurements on Tb(III) and Eu(III) complexes. A detailed optical and chiroptical spectroscopic characterization has been carried out and reveals that the complexes display an efficient luminescence in the visible spectral range accompanied by a strong CPL activity. A value for glum (around 0.1 on the top of the 546 nm band) for the Tb-based complex has been found. This is one of the highest glum values measured up to now for chiral Tb complexes. These results suggest that in principle Tb(bpcd)Cl is suitable to be employed as a CPL bioprobe for relevant analytes in aqueous media.
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MEDLINE
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Revista:
Inorg Chem
Año:
2017
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Article
País de afiliación:
Italia