0000000000287999
AUTHOR
Jérôme Lacour
NMR enantiodifferentiation of triphenylphosphonium salts by chiral hexacoordinated phosphate anions
BINPHAT anion—rather than TRISPHAT—is an efficient NMR chiral shift reagent for triphenylphosphonium salts containing stereogenic centers on the aliphatic side-chain. BINPHAT—rather than TRISPHAT—anion is an efficient NMR (1H and 31P) chiral shift reagent for chiral triphenylphosphonium salts.
Ion-Pairing Effects in the Self-Assembly of a Fluorescent Pseudorotaxane
Herein we report on the self-assembly, in a low polarity solvent, of a pseudorotaxane species comprising binaphthyl-26-crown-8 (BN26C8) as the macrocyclic host and anthracenyl-benzylammonium as the threadlike positively charged guest (ABH+). Absorption and luminescence data reveal a very efficient energy transfer process occurring from the binaphthyl to the anthracene singlet excited states. The self-assembly is highly dependent on the nature of the counteranion confirming the crucial role played by it in the competition between the self-assembly process and the formation of ion pairs (ABH+X-). This behavior can be readily evidenced in dilute solutions from the analysis of the luminescence …
Unusual packing of ET molecules caused by π–π stacking interactions with TRISPHAT molecules in two [ET][TRISPHAT] salts (ET=bis(ethylenedithio)tetrathiafulvalene, TRISPHAT=(tris(tetrachlorobenzenediolato)phosphate(V)))
Abstract The synthesis, structure and physical properties of two new radical salts formed with the organic donor bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF or ET) and a racemic mixture of the chiral anion (tris(tetrachlorobenzenediolato)phosphate(V)) (TRISPHAT) are reported. The structure of the salts (ET)4[TRISPHAT]4 · 3.5H2O (1) and (ET)(TRISPHAT) · CH2Cl2 · CH3CN (2) has been solved by X-ray single crystal diffraction. Unusual packings of ET molecules are obtained in the two structures. The electrical properties indicate that both compounds are insulators. This is in agreement with the isolation of the ET molecules and their complete ionization. On the other hand, the anisotropy of …
Radical cation salts of BEDT-TTF, enantiopure tetramethyl-BEDT-TTF, and TTF-Oxazoline (TTF-Ox) donors with the homoleptic TRISPHAT anion
International audience; The synthesis and crystal structures of five radical cation salts based on the organic donors bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF), racemic ethylenedithio-methyl-oxazoline-tetrathiafulvalene (EDT-TTF-MeOx) and the enantiopure (S,S,S,S) and (R,R,R,R) tetramethyl-bis(ethylenedithio)tetrathiafulvalene (TMBEDT-TTF) and the D3-symmetric anion tris(tetrachlorobenzenediolato)phosphate(V) (TRISPHAT) are reported. The salts are formulated as [BEDT-TTF][(rac)-TRISPHAT]·CH2Cl2 (1), [BEDT-TTF][(rac)-TRISPHAT]·2CH3CN (2), [(rac)-EDT-TTF-Ox][(rac)-TRISPHAT]·CH3CN (3), [(S,S,S,S)-TMBEDT-TTF][(rac)-TRISPHAT]·2CH3CN (4), and [(R,R,R,R)-TMBEDT-TTF][(rac)-TRISPHAT]·2CH3CN (…
Kinetic control in the chiral recognition of three-bladed propellers
The ion pair of the stereolabile C(3)-symmetric, i(+)o proton complex [1H](+) of diaza-macropentacycle 1 and the configurationally stable Delta-TRISPHAT ([Delta-3](-)) anion exists in the form of two diastereomers, namely, [Delta-(1.H)][Delta-3] and [Lambda-(1.H)][Delta-3], the ratio of which, in terms of diastereomeric excess (de) decreases in the order [D(8)]THF (28%)CD(2)Cl(2) (22%)CDCl(3) (20%)[D(8)]toluene (16%)C(6)D(6) (7%)[D(6)]acetone (0%) at thermodynamic equilibrium. Except in the case of [D(6)]acetone, the latter is reached after a period of time that increases from 1 h ([D(8)]THF) to 24 h (CDCl(3)). Moreover, the initial value of the de of [1.H][Delta-3] in CDCl(3), before the t…