Luminescent Eu3+ complexes in acetonitrile solution: Anion sensing and effect of water on the speciation

Piccinelli, Fabio; Leonzio, Marco; Bettinelli, Marco; Melchior, Andrea; Faura, Georgina; Tolazzi, Marilena

doi:10.1016/j.ica.2016.09.047

Cited by 16 publications

(10 citation statements)

References 39 publications

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“…16 We recently studied the coordination chemistry of Eu(III) and Tb(III) ions with ligands carrying the chiral 1,2-diaminocyclohexane (DACH) backbone, which have been suitably modified to form stable complexes in water. [17][18][19][20] In particular, we obtained the water soluble Tb-complex ([Tb(bpcd)(H2O)x] + , chart 1) characterized by strong Tb-based CPL activity upon excitation of the ligand. 20 The chiral H2bpcd (N,N′-bis(2-pyridylmethyl)-trans-1,2-diaminocyclohexane-N,N′diacetic acid) (Chart 1), tightly binds Ln(III) ions, providing a dissymmetric environment, while at the same time leaving 2 -3 sites available for binding to further ancillary ligands.…”

Section: Introductionmentioning

confidence: 99%

A chiral lactate reporter based on total and circularly polarized Tb(iii) luminescence

et al. 2018

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Section: Introductionmentioning

confidence: 99%

A chiral lactate reporter based on total and circularly polarized Tb(iii) luminescence

et al. 2018

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“… 44 Also, for complexes with L , it has been shown that the solvent nature deeply affects the nature of the adducts formed with a variety of ions. 45 In light of these results, it is reasonable to connect the two different CPL signatures (one almost the mirror image of the other; Figures 3 and 4 ) with the degree of dissociation of the anions in the different solvents. In AN, the CPL spectral analysis suggests that (1) in this solvent coexist the species present in both MeOH and DCM and (2) their relative amounts depend on the anion.…”

Section: Resultsmentioning

confidence: 84%

Effect of the Counterion on Circularly Polarized Luminescence of Europium(III) and Samarium(III) Complexes

et al. 2020

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Each enantiopure europium(III) and samarium(III) nitrate and triflate complex of the ligand L , with L = N , N ′-bis(2-pyridylmethylidene)-1,2-( R , R + S , S )-cyclohexanediamine ([Ln L (tta) 2 ]·NO 3 and [Ln L (tta) 2 (H 2 O)]·CF 3 SO 3 , where tta = 2-thenoyltrifluoroacetylacetonate) has been synthesized and characterized from a spectroscopic point of view, using a chiroptical technique such as electronic circular dichroism (ECD) and circularly polarized luminescence (CPL). In all cases, both ligands are capable of sensitizing the luminescence of both metal ions upon absorption of light around 280 and 350 nm. Despite small differences in the total luminescence (TL) and ECD spectra, the CPL activity of the complexes is strongly influenced by a concurrent effect of the solvent and counterion. This particularly applies to europium(III) complexes where the CPL spectra in acetonitrile can be described as a weighed linear combination of the CPL spectra in dichloromethane and methanol, which show nearly opposite signatures when their ligand stereochemistries are the same. This phenomenon could be related to the presence of equilibria interconverting solvated, anion-coordinated complexes and isomers differing by the relative orientation of the tta ligands. The difference between some bond lengths (M–N bonds, in particular) in the different species could be at the basis of such an unusual CPL activity.

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“…On the contrary, although the stereochemistry of the ligands ( rac ‐ L1 or meso ‐ L1 ; figure 13) does not strongly affect the luminescence sensing towards nitrate, [85] it plays an important role in the optical sensing oft he bromide anion. Only meso ‐ L1 is capable to promote the Eu(III) luminescence sensing towards this ion [50] …”

Section: Luminescent Chiral Lanthanide‐based Complexes Containing Tra...mentioning

confidence: 99%

“…Metal speciation can be determined also in non‐aqueous solvents by employing spectroscopic, [47] calorimetric [38,48] and in some cases [49] potentiometric methods. In non‐aqueous media, attention should be paid to the composition of the solution, particularly to the water content, [50,51] as H 2 O molecules can compete with weakly coordinating solvents for the metal ion and to the possible coordination of the counterions [38] …”

Section: Introductionmentioning

confidence: 99%

Lanthanide‐Based Complexes Containing a Chiral trans‐1,2‐Diaminocyclohexane (DACH) Backbone: Spectroscopic Properties and Potential Applications

et al. 2021

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In this minireview, we give an overview on the use of the chiral molecule trans‐1,2‐diaminocyclohexane (DACH) in several fields of application. This chiral backbone is present in a variety of metal complexes which are employed in (enantioselective) catalysis, chiral discrimination, molecular recognition and supramolecular chemistry. Metal extraction and biochemical and pharmaceutical applications also use the DACH molecule. This contribution is particularly focused on the interesting chemical‐physical properties discussed so far in the literature concerning lanthanide‐based complexes containing chiral ligands characterized by the presence of DACH in the structure. In particular, the interconnection between luminescence (total and circularly polarized), structure and thermodynamics of Eu(III), Tb(III) and Sm(III) complexes will be discussed also in light of their use as optical or chiroptical probes for the sensing of important analytes dissolved in aprotic and protic polar solvents. Several complexes show potential interest in the solid state as phosphors for light emitting devices or for the detection of volatile organic compounds.

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Luminescent Eu3+ complexes in acetonitrile solution: Anion sensing and effect of water on the speciation

Cited by 16 publications

References 39 publications

A chiral lactate reporter based on total and circularly polarized Tb(iii) luminescence

A chiral lactate reporter based on total and circularly polarized Tb(iii) luminescence

Effect of the Counterion on Circularly Polarized Luminescence of Europium(III) and Samarium(III) Complexes

Lanthanide‐Based Complexes Containing a Chiral trans‐1,2‐Diaminocyclohexane (DACH) Backbone: Spectroscopic Properties and Potential Applications

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