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Miniaturized microreactors enable photochemistry with laser irradiation in flow mode to convert azidobiphenyl into carbazole with high efficiency

Soccer goes BOXing: synthetic access to novel [6:0] hexakis[(bisoxazolinyl)methano]fullerenes

The syntheses of [6:0] hexakis[(bisoxazolinyl)methano]fullerenes are presented. Two derivatives could be directly obtained using conditions developed by the Sun group. For the remaining products, a two stage protocol had to be developed. All compounds we obtained in synthetically useful scales and were purified via column chromatography with standard achiral phase. These new fullerene adducts bear six metal-chelation sites which are aligned in the three orthogonal space directions and are disposed on a completely rigid scaffold. First experiments indicate that the generation of six-fold metal-complexes is possible with these structures. This makes them very appealing as ligands in asymmetric catalysis and as building blocks in higher supra-molecular assemblies

Photochemistry with laser radiation in condensed phase using miniaturized photoreactors

Miniaturized microreactors enable photochemistry with laser irradiation in flow mode to convert azidobiphenyl into carbazole with high efficiency

Tetrathiafulvalene-oxazoline ligands in the iridium catalyzed enantioselective hydrogenation of arylimines

International audienceCationic iridium complexes based on enantiomerically pure tetrathiafulvalene-oxazoline ligands have been used in the asymmetric hydrogenation of N-(phenylethylidene)aniline. Complete conversions with ee's up to 68% could be reached in the case of the TTF-phosphinooxazoline (TTF-PHOX) ligands

Synthesis of Archaeal Bipolar Lipid Analogues: A Way to Versatile Drug/Gene Delivery Systems

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Chiral tetrathiafulvalene based phosphine- and thiomethyl-oxazoline ligands. Evaluation in palladium catalysed asymmetric allylic alkylation

International audienceNew chiral redox active ligands based on ethylenedithio-tetrathiafulvalene (EDT-TTF) bearing racemic or optically pure oxazolines have been synthesised. These auxiliaries possess an additional functionality on the TTF unit, namely a thiomethyl residue or a diphenylphosphino moiety. All ligands have been tested in asymmetric allylic substitutions. The enantioselectivity reached is 85% ee

OS vs. NS intramolecular nonbonded interactions in neutral and radical cation salts of TTF-oxazoline derivatives: synthesis, theoretical investigations, crystalline structures, and physical properties

Racemic and enantiopure ethylenedithio-tetrathiafulvalene-thiomethyl-oxazoline (EDT-TTF-(SMe)-OX) derivatives have been synthesized. Single-crystal X-ray diffraction analyses reveal the establishment of OS nonbonded interactions, unprecedented in the TTF series, characterized by short SO distances and linear OSMe motifs. Theoretical calculations at the DFT/B3LYP level on a model molecule demonstrate that both possible planar s-trans (OS interaction) and s-cis (NS interaction) conformations are energy minima, separated by an extremely weak energy gap. The energy barrier corresponding to the equilibrium between the two forms has been also estimated from DFT calculations, as well as their relative stability in the radical cation state of the TTF. According to the latter, there is a slight tendency towards the enhancement of the NS interactions. Following the predictions of the theoretical calculations, the coexistence of both OS and NS nonbonded interactions is observed in two mixed valence radical cation salts of the racemic TTF with the dianionic cluster Mo6Cl14, prepared upon electrocrystallization. Interestingly, the ratio TTF : dianion is finely tuned by the choice of the electrocrystallization solvent. Physical measurements such as electrical conductivity and thermoelectric power on single crystals combined with magnetic susceptibility data in one case and extended Hückel tight-binding calculations demonstrate and rationalize the semiconducting behavior of both mixed valence salts. This study demonstrates that intramolecular NS and OS interactions can efficiently modulate and direct in the TTF series the occurrence of original solid-state structures provided with physical properties

Order versus disorder in chiral tetrathiafulvalene-oxazoline radical-cation salts: structural and theoretical investigations and physical properties.

International audienceElectrocrystallization experiments with the chiral ethylenedithio-tetrathiafulvalene-methyl-oxazoline (EDT-TTF-OX) donors (R)-, (S)-, and (rac)-1 have provided two series of mixed-valence salts with the PF(6) (-) and [Au(CN)(2)](-) anions. Within each series the cell parameters are the same for the three R, S, and rac compounds, except for the space group, which is centrosymmetric triclinic P$\bar 1$ for the racemic forms and noncentrosymmetric P1 for the enantiopure salts. In the racemic salt [(rac)-1](2)PF(6) the two enantiomers crystallize disordered on the same crystallographic site with a site occupational factor of 0.6:0.4, whereas this type of disorder is not possible in the enantiopure salts. Both s-cis and s-trans conformations, when taking into account the mutual orientation of the TTF and oxazoline moieties, are present in this first series. In sharp contrast, in the series of salts [1](2)[Au(CN)(2)], only the s-trans conformation is observed with no structural disorder. Theoretical calculations at the DFT level of theory revealed a very small energy difference between the two stable planar s-cis and s-trans conformations, which are both energy minima in either neutral or oxidized states. Single-crystal conductivity measurements showed metallic-like behavior for all the salts down to 220-250 K with a smooth increase in resistivity at lower temperatures. The conductivity at room temperature is 5 S cm(-1) for [(rac)-1](2)PF(6), in which disorder was observed, whereas for [(R)-1](2)PF(6) and [(S)-1](2)PF(6) the average value is around 100 S cm(-1). In the second series of salts the conductivity at room temperature is 125-130 S cm(-1) for [(rac)-1](2)[Au(CN)(2)] and [(R)-1](2)[Au(CN)(2)]. Extended Hückel band structure calculations revealed identical features for the three salts of the [1](2)[Au(CN)(2)] series and are consistent with the electronic structures of quasi-one-dimensional conductors

Avarvari radical cation salts of BEDT-TTF, enantiopure tetramethyl-BEDT-TTF, and TTF-oxazoline (TTF-Ox) donors with the homoleptic TRISPHAT anion

International audienceThe 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 (5). The donors are fully oxidized and self-assemble in dyads inserted in the channels generated by the packing of the TRISPHAT anions. Magnetic and EPR measurements performed on compounds 1 and 2 clearly indicate weak interactions within the dimers in compound 1, characterized by a very narrow line in the EPR spectrum, while the radicals are strongly coupled in compound 2