New redox active ligands involving a tetrathiafulvalene vinylogue backbone

Guerro, Michel; Pham, Ngoc Ha T.; Massue, Julien; Bellec, Nathalie; Lorcy, Dominique

doi:10.1016/j.tet.2008.03.032

Cited by 21 publications

(13 citation statements)

References 37 publications

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“…Two resonances (18H each) for the o-and p-tertbutyl groups appear at −5.38 and 37.66 ppm, respectively, along with a smaller resonance (2H) shifted drastically to −248.69 ppm for the aryl−CH protons. This extreme upfield shift has been noted previously for uranium species bearing radical ligands, 26,28,29 leading to the assignment of the green product as (DOPO sq )UI 2 , with a semiquinone radical ligand by analogy to ( R isq)UI 3 (THF) 2 .…”

supporting

confidence: 68%

“…Quantification of the liberated THF was possible by integration against a mesitylene internal standard. This experiment established the presence of two equivalents of THF for each equivalent of (DOPO sq )UI 2 , leading to the more accurate assignment of (DOPO sq )-UI 2 (THF) 2 (2).…”

mentioning

confidence: 74%

“…In this case, there are no additional electrons on uranium that can reduce the ligand, thus eliminating ambiguity of ligand oxidation states. Treating an orange toluene solution of UO 2 [N-(SiMe 3 ) 2 ] 2 (THF) 2 12 with 2 equiv of HDOPO q resulted in a color change to emerald green (eq 1). The concentration of this solution facilitated precipitation of a dark green powder assigned as (DOPO q ) 2 UO 2 (1) in high yield (86%).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…10 For instance, the bidentate amidophenolate ligands in ( R ap) 2 U(THF) 2 can mediate oxidative addition of chlorine or iodine at monomeric U(IV) complexes, where the two reducing equivalents necessary for bond cleavage are derived from the ligand. Thus, radical iminosemiquinone ligands ( R isq) support the products from oxidative addition, which are dimeric, [( R isq) 2 UCl] 2 (μ-Cl) 2 , and monomeric, ( R isq) 2 UI 2 . 9 Alternately, radical reductive elimination of bibenzyl occurs from tetrabenzyluranium using the iminoquinone form of the ligand.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Preparation of (DOPO sq )UI 2 (THF) 2 (2). A 20 mL scintillation vial was charged with UI 3 (THF) 4 (0.083 g, 0.091 mmol) and KDOPO q (THF) (0.050 g, 0.091 mmol).…”

Section: ■ Introductionmentioning

confidence: 99%

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Spectroscopic and Structural Elucidation of Uranium Dioxophenoxazine Complexes

et al. 2015

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Uranium derivatives of a redox-active, dioxophenoxazine ligand, (DOPO(q))2UO2, (DOPO(sq))UI2(THF)2, (DOPO(cat))UI(THF)2, and Cp*U(DOPO(cat))(THF)2 (DOPO = 2,4,6,8-tetra-tert-butyl-1-oxo-1H-phenoxazin-9-olate), have been synthesized from U(VI) and U(III) starting materials. Full characterization of these species show uranium complexes bearing ligands in three different oxidation states. The electronic structures of these complexes have been explored using (1)H NMR and electronic absorption spectroscopies, and where possible, X-ray crystallography and SQUID magnetometry.

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supporting

confidence: 68%

mentioning

confidence: 74%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

“…Preparation of (DOPO sq )UI 2 (THF) 2 (2). A 20 mL scintillation vial was charged with UI 3 (THF) 4 (0.083 g, 0.091 mmol) and KDOPO q (THF) (0.050 g, 0.091 mmol).…”

Section: ■ Introductionmentioning

confidence: 99%

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Spectroscopic and Structural Elucidation of Uranium Dioxophenoxazine Complexes

et al. 2015

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Dye‐Sensitized Solar Cells Based on (Donor‐π‐Acceptor)₂ Dyes With Dithiafulvalene as the Donor

Lee¹,

Hsu²,

Liao³

et al. 2014

Chemistry An Asian Journal

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Dipolar metal-free sensitizers (D-π-A; D=donor, π=conjugated bridge, A=acceptor) consisting of a dithiafulvalene (DTF) unit as the electron donor, a benzene, thiophene, or fluorene moiety as the conjugated spacer, and 2-cyanoacrylic acid as the electron acceptor have been synthesized. Dimeric congeners of these dyes, (D-π-A)(2), were also synthesized through iodine-induced dimerization of an appropriate DTF-containing segment. Dye-sensitized solar cells (DSSCs) with the new dyes as the sensitizers have cell efficiencies that range from 2.11 to 5.24 %. In addition to better light harvesting, more effective suppression of the dark current than the D-π-A dyes is possible with the (D-π-A)(2) dyes.

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