A Hexakis Terpyridine-Fullerene Ligand in Six-Fold Ruthenium, Iridium, and Iron Complexes: Synthesis and Electrochemical Properties.

An unprecedented straightforward route to six-fold terpyridine ligands around C60 , the latter being regioselectively functionalized in pseudo-octahedral positions using a six-fold Bingel reaction, is reported. Ruthenium, iridium, and iron complexes have been synthesized, and unambiguously characterized by NMR, MS, and cyclic voltammetry.

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.

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

Electrocrystallization 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.

Chiral molecular metals: syntheses, structures, and properties of the AsF(6)(-) salts of racemic (+/-)-, (R)-, and (S)-tetrathiafulvalene-oxazoline derivatives.

A metallic behavior characterizes a first complete series of 2:1 AsF6- mixed-valence chiral salts of (R)-, (S)-, and racemic (+/-)-tetrathiafulvalene methyl-oxazoline derivatives. The enhanced conductivity of the pure enantiomeric salts, when compared with that of the racemic one, is the likely consequence of the structural disorder observed in the latter.

Tetrathiafulvalene based phosphino-oxazolines: a new family of redox active chiral ligands.

Reaction of the lithium salt of EDT-TTF-2-(4-methyl)oxazoline with chloro-diphenylphosphine afforded the novel redox active chiral chelating ligands, EDT-TTF-phosphino-oxazolines, for which a palladium (II) dichloride complex was synthesized and structurally characterized.