Synthesis and crystal structure of the Sm(ButNCHCHNBut)2(bpy) complex

Petrovskaya, Tatyana V.; Fedyushkin, I. L.; Bochkarev, M. N.; Shumann, G.; Veimann, R.

doi:10.1007/bf02495133

Cited by 10 publications

(11 citation statements)

References 10 publications

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“…However, replacement of dme with toluene leads to a color change to red. Complex (dpp-Bian)Eu II (bipy) 2 (9) has been isolated as a deep red crystal in 57% yield (Scheme 1). In contrast, related ytterbium complex (dpp-Bian)Yb II (dme) 2 (4) reacts in dme with bipy instantly on mixing the reagents.…”

Section: ■ Results and Discussionmentioning

confidence: 71%

“…As far as we know compound ( t Bu-dad) 2 Sm III (bipy) is the only example of the lanthanide complex containing two different redox-active ligands. Besides the redox-isomerism associated with reversible metal-to-ligand electron transfer, another type of electronic transformation may be expected in such systemsintramolecular redox process between two ligands.…”

Section: Resultsmentioning

confidence: 99%

“…Synthesis and Characterization of (dpp-Bian)-Eu II (bipy) 2 ( 9), (dpp-Bian)Yb II (bipy)(bipy − ) (10), (dpp-Bian)Eu II (mes-dad)(dme) (11), and (dpp-Bian)Eu II -(OC 6 H 2 -3,6-Bu t 2 -2-OEt)(dme) (12). As far as we know compound (tBu-dad) 2 Sm III (bipy) 9 is the only example of the lanthanide complex containing two different redox-active ligands. Besides the redox-isomerism associated with reversible metal-to-ligand electron transfer, another type of electronic transformation may be expected in such systemsintramolecular redox process between two ligands.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Ytterbium and Europium Complexes of Redox-Active Ligands: Searching for Redox Isomerism

et al. 2017

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The reaction of (dpp-Bian)Eu(dme) (3) (dpp-Bian is dianion of 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene; dme is 1,2-dimethoxyethane) with 2,2'-bipyridine (bipy) in toluene proceeds with replacement of the coordinated solvent molecules with neutral bipy ligands and affords europium(II) complex (dpp-Bian)Eu(bipy) (9). In contrast the reaction of related ytterbium complex (dpp-Bian)Yb(dme) (4) with bipy in dme proceeds with the electron transfer from the metal to bipy and results in (dpp-Bian)Yb(bipy)(bipẏ) (10) - ytterbium(III) derivative containing both neutral and radical-anionic bipy ligands. Noteworthy, in both cases dianionic dpp-Bian ligands retain its reduction state. The ligand-centered redox-process occurs when complex 3 reacts with N,N'-bis[2,4,6-trimethylphenyl]-1,4-diaza-1,3-butadiene (mes-dad). The reaction product (dpp-Bian)Eu(mes-dad)(dme) (11) consists of two different redox-active ligands both in the radical-anionic state. The reduction of 3,6-di-tert-butyl-4-(3,6-di-tert-butyl-2-ethoxyphenoxy)-2-ethoxycyclohexa-2,5-dienone (the dimer of 2-ethoxy-3,6-di-tert-butylphenoxy radical) with (dpp-Bian)Eu(dme) (3) caused oxidation of the dpp-Bian ligand to radical-anion to afford (dpp-Bian)(ArO)Eu(dme) (ArO = OCH-3,6-tBu-2-OEt) (12). The molecular structures of complexes 9-12 have been established by the single crystal X-ray analysis. The magnetic behavior of newly prepared compounds has been investigated by the SQUID technique in the range 2-310 K. The isotropic exchange model has been adopted to describe quantitatively the magnetic properties of the exchange-coupled europium(II) complexes (11 and 12). The best-fit isotropic exchange parameters are in good agreement with their density functional theory-computed counterparts.

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Section: ■ Results and Discussionmentioning

confidence: 71%

Section: Resultsmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

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Ytterbium and Europium Complexes of Redox-Active Ligands: Searching for Redox Isomerism

et al. 2017

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“…It should be noted that the tendency of lanthanides to form complexes of the [Ln] 2+ [L] 27 type even in the presence of the free uncharged ligand is also observed in the case of other ligands (such as bipy } or DAD) exhibiting polyvalence. 107 The mode of bonding of lanthanide with arene ligands can vary from Z 2 to Z 6 . The Ln atom can be coordinated both at the plane of the arene ligand and at its edge.…”

Section: Discussionmentioning

confidence: 99%

Arene complexes of rare-earth metals

Bochkarev¹

2000

Russ. Chem. Rev.

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“…This six-coordinate Sm 3+ or Eu 3+ is unusual but not without precedent. [55][56][57][58] The symmetry of the [Sm((S)-BINAPO) 2 (OTf) 2 ] + (Figure 4), and site symmetry at the Sm (or Eu) is C 2 , a chiral point group The chiral arrangement of the BINAPO and OTf − ligands around the metal center satisfies the requirement for a static coupling mechanism leading to dipole and rotatory strengths for magnetic-dipole allowed CPL transitions 18,27 in Eu 3+ and Sm 3+ . Because the BINAPO ligands have π → π* transitions, the dipole and rotatory strengths could also derive from the dynamic coupling mechanism between the Eu 3+ or Sm 3+ electric quadrupole (or larger multipole) moment and ligand π → π* transitions.…”

Section: Calculationsmentioning

confidence: 99%

Circularly polarized luminescence of Sm (III) and Eu (III) complexes with chiral ligand (R/S)‐BINAPO

et al. 2019

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Luminescent lanthanide (III) ions have been exploited for circularly polarized luminescence (CPL) for decades. However, very few of these studies have involved chiral samarium (III) complexes. Complexes are prepared by mixing axial chiral ligands (R/S))-2,2'-bis(diphenylphosphoryl)-1,1′-binaphthyl (BINAPO) with europium and samarium Tris (trifluoromethane sulfonate) (Eu (OTf) 3 and Sm (OTf) 3 ). Luminescence-based titration shows that the complex formed is Ln((R/S)-BINAPO) 2 (OTf) 3 , where Ln = Eu or Sm. The CPL spectra are reported for Eu((R/S)-BINAPO) 2 (OTf) 3 and Sm((R/S)-BINAPO) 2 (OTf) 3 .The sign of the dissymmetry factors, g em , was dependent upon the chirality of the BINAPO ligand, and the magnitudes were relatively large. Of all of the complexes in this study, Sm((S)-BINAPO) 2 (OTf) 3 has the largest g em = 0.272, which is one of the largest recorded for a chiral Sm 3+ complex. A theoretical three-dimensional structural model of the complex that is consistent with the experimental observations is developed and refined. This report also shows that (R/S)-BINAPO are the only reported ligands where g em (Sm 3+ ) > g em (Eu 3+ ).

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Synthesis and crystal structure of the Sm(ButNCHCHNBut)2(bpy) complex

Cited by 10 publications

References 10 publications

Ytterbium and Europium Complexes of Redox-Active Ligands: Searching for Redox Isomerism

Ytterbium and Europium Complexes of Redox-Active Ligands: Searching for Redox Isomerism

Arene complexes of rare-earth metals

Circularly polarized luminescence of Sm (III) and Eu (III) complexes with chiral ligand (R/S)‐BINAPO

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