Lanthanide(III) trifluoromethanesulfonate complexes in anhydrous acetonitrile

Bernardo, Plinio Dí; Choppin, Gregory R.; Portanova, Roberto; Zanonato, Pier Luigi

doi:10.1016/s0020-1693(00)91459-2

Cited by 55 publications

(36 citation statements)

References 17 publications

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“…The Ba±Ba distances vary by a maximum of 1.643 A Ê with Ba1±Ba2 distances of 6.163(5), Ba1±Ba2' of 6.827(5), and the Ba2±Ba2' distance which is 5.184(5) A Ê long ( Figure 2). The IR spectra of the starting compound Ba(OTf) 2 and 1 clearly show the presence of differently bridging triflate anions as their S±O-stretching bands are slightly shifted and multiplied compared to purely ionic triflate salts like AgSO 3 CF 3 [12] or NH 4 SO 3 CF 3 [13] ( Table 2). The l 3 -bridging tridentate triflate ligand has approximately the same C 3v symmetry as in the free ion [14,15].…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Crystal Structure of the One-Dimensional Polymer Compound∞1{[Ba(OTf)2(thf)3]2[Ba(OTf)2(thf)2]} (OTf = CF3SO3-) - Excerpts from a Three-Dimensional Structure as an Access to New Materials?

Fromm¹,

Bérnardinelli

2001

Z. anorg. allg. Chem.

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Ba(CF 3 SO 3 ) 2 reacts with the O-donor ligand THF to yield the coordination compound 1. The title compound can be described as a one-dimensional excerpt from the higher-dimensional crystal structure of Ba(CF 3 SO 3 ) 2 , stabilized by THF. This example for the concept of formally ªcut-ting outº structural elements from a three-dimensional solid state compound confirms and can be compared to the case of the structural ªgenealogy treeº of BaI 2 . This could be an efficient approach for new materials with highly anisotropic properties.

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Section: Resultsmentioning

confidence: 99%

Synthesis and Crystal Structure of the One-Dimensional Polymer Compound∞1{[Ba(OTf)2(thf)3]2[Ba(OTf)2(thf)2]} (OTf = CF3SO3-) - Excerpts from a Three-Dimensional Structure as an Access to New Materials?

Fromm¹,

Bérnardinelli

2001

Z. anorg. allg. Chem.

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“…The isoelectronic Gd 3+ and Eu 2+ ions have been chosen because they induce by far the strongest relaxation enhancement. Di Brenardo et al 47 showed by IR measurements that, in the acetonitrile solution of the Lu(CF 3 SO 3 ) 3 complex at least one [CF 3 SO 3 ]anion is coordinated to the metal centre. Moreover, our IR measurements on the Eu(CH 3 CN) 2 (CF 3 SO 3 ) 2 complex in anhydrous acetonitrile also revealed vibrational bands for uncoordinated and coordinated triflates.…”

Section: Conductivity Measurementsmentioning

confidence: 99%

Synthesis, structures and characterisations of truly homoleptic acetonitrile Ln3+ complexes in solid state and in solution

et al. 2009

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Total halide abstraction from LnCl3 by Ag[Al(OC(CF3)3)4]/CH3CN has been confirmed for a series of lanthanide metal ions by the structural characterization of [Ln(CH3CN)n][Al(OC(CF3)3)4]3 (n=9, Ln3+=Nd, Eu, Gd, Dy; n=8, Ln3+=Tm) complexes. Evidence for the very low coordinating ability of the [Al(OC(CF3)3)4]- anion towards Ln3+ ions is provided in the solid state (X-ray, IR and Raman spectroscopy) and in anhydrous acetonitrile solution (conductivity, EPR and NMR measurements). In the solid state homoleptic nine-coordinated acetonitrile species are characteristic for lanthanides for the beginning (Nd) and the middle (Eu, Gd, Dy) of the Ln series, with a mono-capped square antiprismatic arrangement of the N donor atoms around the metal centres; while for those from the end of the series (Tm) eight-coordinated species are representative with a square antiprismatic arrangement. In anhydrous acetonitrile solution, conductivity measurements revealed 3:1 electrolyte types for all compounds. EPR and 19F NMR line broadening measurements attest lanthanide complexes free of any coordinating [Al(OC(CF3)3)4]- anion.

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“…35 Lanthanide triflate salts have been shown to be completely dissociated only at concentrations lower than 0.05 mmol dm −3 in anhydrous AN, 36 while at high salt concentrations (∼30 mmol dm −3 ) the prevalent species in AN are the undissociated salt and the 1 : 1 electrolyte Ln(OTf ) 2 + . 37 At this concentration, the release of triflate ions does not occur in AN, even in the presence of a strong N-donor such as n-butylamine (DN = 42), 18 which binds the lanthanide ions only through a preferential loss of coordinated solvent molecules. 14 The log β 1 values found with L1-L4 are always significantly lower for the nitrate complex with respect to the triflate one, indicating that the coordination of the first ligand is disfavored by the presence of nitrate ions.…”

Section: Speciationmentioning

confidence: 99%

Structural, optical and sensing properties of novel Eu(iii) complexes with furan- and pyridine-based ligands

et al. 2015

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A new family of imine and amine-based racemic ligands containing furan or pyridine as an aromatic donating ring [N,N′-bis(2-pyridylmethylidene)-1,2-(R,R + S,S)-cyclohexanediamine, L1; N,N′-bis(2-furanylmethylidene)-1,2-(R,R + S,S)-cyclohexanediamine, L2; N,N′-bis(2-pyridylmethyl)-1,2-(R,R + S,S)-cyclohexanediamine, L3; and N,N′-bis(2-furanylmethyl)-1,2-(R,R + S,S)-cyclohexanediamine, L4] and their trifluoromethanesulphonate (CF3SO3(−), OTf(−)) and nitrate Eu(III) complexes is studied in acetonitrile (AN) solution. The stoichiometry and stabilities of the formed complexes are obtained by means of spectrophotometric titrations: when Eu(III) triflate is used as a starting salt, two mononuclear species (1:1 and 1:2) are detected, while only the 1:1 complex is observed when the nitrate salt is employed. The stability of these complexes, as well as the geometry of their Eu(III) environment, is significantly dependent on the nature of the ligand employed (imine or amine, furan or pyridine-based). DFT calculations show that all donor atoms are coordinated to the metal ion in the 1:1 EuL(L = L1–L4) species and suggest that the higher stability of the complexes with L1 and L2 with respect to L3 and L4 is mostly due to the higher degree of preorganization of the former species. The optical response of the imine-based L1 and L2 Eu complexes, produced by NO3(−) coordination, has been studied in order to assess their application as sensing devices. With both ligands, an increase of the emission intensity on the addition of the nitrate ion is observed. This is higher for the EuL2 complex and underlines the important role of the nature of the heteroaromatic ring. Finally, it is worth noting that an efficient energy transfer process from the ligand to the metal is present in the case of the 1:1 triflate Eu(III) complex with the ligand L1.

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Lanthanide(III) trifluoromethanesulfonate complexes in anhydrous acetonitrile

Cited by 55 publications

References 17 publications

Synthesis and Crystal Structure of the One-Dimensional Polymer Compound∞1{[Ba(OTf)2(thf)3]2[Ba(OTf)2(thf)2]} (OTf = CF3SO3-) - Excerpts from a Three-Dimensional Structure as an Access to New Materials?

Synthesis and Crystal Structure of the One-Dimensional Polymer Compound∞1{[Ba(OTf)2(thf)3]2[Ba(OTf)2(thf)2]} (OTf = CF3SO3-) - Excerpts from a Three-Dimensional Structure as an Access to New Materials?

Synthesis, structures and characterisations of truly homoleptic acetonitrile Ln3+ complexes in solid state and in solution

Structural, optical and sensing properties of novel Eu(iii) complexes with furan- and pyridine-based ligands

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