Emmanuel Aubert

Electrogeneration of highly methylated mesoporous silica thin films with vertically-aligned mesochannels and electrochemical monitoring of mass transport issues

In this work, we describe a versatile approach to generate highly methylated mesoporous silica films exhibiting hexagonally-packed one-dimensional mesochannels oriented uniquely perpendicular to the underlying support. It involves the electro-assisted self-assembly (EASA) of tetraethoxysilane (TEOS) and methyltriethoxysilane (MTES) with cetyltrimethylammonium bromide (CTAB) under potential control. Transmission electron microscopy and grazing-incidence X-ray diffraction indicate that high level of ordering and vertical alignment of mesopores can be maintained at rather high MTES contents (up to 50–60 mol% with respect to total precursors in the starting sol). The rate of film growth decreased concomitantly to increasing the MTES/TEOS ratio, resulting in thinner films for higher functionalization degrees. This also led to more hydrophobic films (after template extraction), which tended to become less permeable to aqueous phase solutes, as pointed out qualitatively and quantitatively by several electrochemical methods and various redox probes. Effective rate constants for electron transfer were found to be several orders of magnitude higher than for other thin silica films on electrodes, explained by preferential porosity orientation.

Electrochemically assisted generation of highly ordered azide-functionalized mesoporous silica for oriented hybrid films.

One key challenge in inorganic mesoporous films is the development of oriented mesostructures with vertical channels, and even more challenging is their functionalization while maintaining accessible the selected surface groups. Combining the electrochemically assisted deposition of ordered and oriented azide-functionalized mesoporous silica with alkyne-azide click chemistry enables such nanostructured and vertically aligned hybrid films to be obtained with significant amounts of active organic functional groups, as illustrated for ferrocene and pyridine functions. A good level of mesostructural order was obtained, namely up to 40% of organosilane in the starting sol. The method could be applied to a wide variety of functional groups, thus offering numerous new opportunities for applications in various fields.

Charge‐Assisted Halogen Bonding: Donor–Acceptor Complexes with Variable Ionicity

Charge-assisted halogen bonding is unambiguously revealed from structural and electronic investigations of a series of isostructural charge-transfer complexes derived from iodinated tetrathiafulvalene and tetracyanoquinodimethane derivatives, (EDT-TTFI2)2(TCNQF(n)), n=0-2, which exhibit variable degrees of ionicity. The iodinated tetrathiafulvalene derivative, EDT-TTFI2, associates with tetracyanoquinodimethane (TCNQ) and its derivatives of increasing reduction potential (TCNQF, TCNQF2) through highly directional C-I⋅⋅⋅N≡C halogen-bond interactions. With the less oxidizing TCNQ acceptor, a neutral and insulating charge-transfer complex is isolated whereas with the more oxidizing TCNQF2 acceptor, an ionic, highly conducting charge-transfer salt is found, both of 2:1 stoichiometry and isostructural with the intermediate TCNQF complex, in which a neutral-ionic conversion takes place upon cooling. A correlation between the degree of charge transfer and the C-I⋅⋅⋅N≡C halogen-bond strength is established from the comparison of the structures of the three isostructural complexes at temperatures from 300 to 20u2005K, thus demonstrating the importance of electrostatics in the halogen-bonding interaction. The neutral-ionic conversion in (EDT-TTFI2)2(TCNQF) is further investigated through the temperature dependence of its magnetic susceptibility and the stretching modes of the C≡N groups.

Periodic projector augmented wave density functional calculations on the hexachlorobenzene crystal and comparison with the experimental multipolar charge density model.

The projector augmented wave (PAW) methodology has been used to calculate a high precision electron density distribution ρ(r) for the hexachlorobenzene crystal phase. Implementing the calculation of the crystallographic structure factors in the VASP code has permitted one to obtain the theoretical multipolar ρ(r). This electron density is compared with both the DFT electron density and the experimental multipolar model obtained from high-resolution X-ray diffraction data. This comparison has been carried out in intra- and intermolecular regions within the framework of the quantum theory of atoms-in-molecules (QTAIM) developed by Bader and co-workers. The characterization of the electron density in both C-Cl and Cl···Cl regions, as well as within the atomic basins, shows similar features for the three models. As a consequence, the observation of charge depletion and charge concentration regions around the halogen nuclei (along the C-Cl bonding axis and in the perpendicular plane, respectively) underlines the nature of halogen bonding in terms of electrophilic and nucleophilic interactions.

Synthesis of polyhalogenated 4,4'-bipyridines via a simple dimerization procedure.

Polyhalogenated 4,4-bipyridines were conveniently synthesized in a single step starting from dihalopyridines. A mechanism was proposed on the basis of experiments performed with 2-chloro-5-bromopyridine 1a. 2-Chloro-4-lithio-5-bromopyridine A1 was produced via ortholithiation of 1a by using either LDA or t-BuLi bases. When LDA was used, dimer 3a containing two chlorines and two bromine atoms was formed predominantly accompanied by several byproducts whose structure and mechanism of formation are discussed. In the case of t-BuLi, although the major product was 2-chloropyridine 7, a new pyridone product 8 was formed that is probably the result of the dihydropyridine intermediate hydrolysis. The dimerization procedure involving LDA was employed to prepare a large number of halogenated 4,4-bipyridines in moderate to good yields. In some specific cases, halogenated 3,4 and 2,4-bipyridines were obtained in lower yields and their structures were unambiguously assigned by X-ray diffraction analysis.

High-performance liquid chromatography enantioseparation of atropisomeric 4,4′-bipyridines on polysaccharide-type chiral stationary phases: Impact of substituents and electronic properties

The high performance liquid chromatography (HPLC) enantioseparation of eleven atropisomeric 4,4-bipyridines was performed in the normal and polar organic phase mode using three cellulose-based chiral stationary phases (CSPs), namely Lux Cellulose-1, Lux Cellulose-2, Lux Cellulose-4, and two amylose-based CSPs, Chiralpak AD-H and Lux Amylose-2. n-Hexane/2-propanol mixtures and pure ethanol were employed as mobile phases. The combined use of Chiralpak AD-H and Lux Cellulose-2 allowed to enantioseparate all the considered bipyridines. Ten bipyridines were enantioseparated at the multimilligram level allowing the elution sequence determination of the enantiomers as well as their future use for the preparation of homochiral metal organic frameworks (MOFs). Moreover, the performance of the CSPs regarding the same bipyridine was different and dependent on the backbone as well as on the side chain of the polymer. The impact of substitution pattern, shape and electronic properties of the molecules on the separation behavior was investigated through the evaluation of retention factors (k), separation factors (α), resolution (R(s)) and molecular properties determined using density functional theory (DFT) calculations. In this regard, the substituents at the 3,3,5,5 positions of the 4,4-bipyridyl rings exhibited a pivotal role on the enantioseparation.

Insights into the impact of shape and electronic properties on the enantioseparation of polyhalogenated 4,4'-bipyridines on polysaccharide-type selectors. Evidence of stereoselective halogen bonding interactions.

Starting from the high-performance liquid chromatography (HPLC) enantioseparation data collected by using twelve polyhalogenated 2,2-dichloro-3-substituted-5,5-dihalo-4,4-bipyridines as test probes on seven polysaccharide-based chiral stationary phases (CSPs) under multimodal elution, the impact of substitution pattern, shape and electronic properties of the molecules on the separation behaviour was investigated through the evaluation of the chromatographic parameters (k, α, Rs) and molecular properties determined by means of quantum chemistry calculations. The computational/chromatographic screening furnished relevant structure-chromatographic behaviour relationships and some molecular interactions involved in the chiral discrimination process could be identified. In particular, a halogen bonding interaction (I(.)O) could reasonably explain the high enantioseparation (α=1.80, Rs=8.2) observed for the 2,2-dichloro-3,5-diiodo-5-bromo-4,4-bipyridine on Lux Cellulose-1. To the best of our knowledge, this is the first report supporting the involvement of a stereoselective halogen bonding interaction in polysaccharide-based CSPs. Moreover, having at disposal a sufficient set of data, the unknown absolute configurations of the eluted enantiomers of 3-methyl-, 3-thiomethyl- and 3-diphenylphosphinoyl-2,2-dichloro-5,5-dibromo-4,4-bipyridines could be deduced by chromatographic correlation with the enantiomer elution order (EEO) of the related compounds of known absolute configuration.

Synthesis, Resolution, and Absolute Configuration of Chiral 4,4′-Bipyridines

A chiral polyhalogenated 4,4-bipyridine derivative is described allowing an easy access to a new family of chiral 4,4-bipyridines by site-selective cross-coupling reactions. The absolute configurations of all the HPLC separated enantiomers were determined by X-ray diffraction and electronic circular dichroism coupled with time-dependent density functional theory calculations.

Optimization of the HPLC enantioseparation of 3,3′‐dibromo‐5,5′‐disubstituted‐4,4′‐bipyridines using immobilized polysaccharide‐based chiral stationary phases

The HPLC enantioseparation of nine atropisomeric 3,3,5,5-tetrasubstituted-4,4-bipyridines was performed in normal and polar organic (PO) phase modes using two immobilized polysaccharide-based chiral columns, namely, Chiralpak IA and Chiralpak IC. The separation of all racemic analytes, the effect of the chiral selector, and mobile phase (MP) composition on enantioseparation and the enantiomer elution order (EEO) were studied. The beneficial effect of nonstandard solvents, such as tetrahydrofuran (THF), dichloromethane (DCM), and methyl t-butyl ether on enantioseparation was investigated. All selected 4,4-bipyridines were successfully enantioseparated on Chiralpak IA under normal or PO MPs with separation factors from 1.14 to 1.70 and resolutions from 1.3 to 6.5. Two bipyridines were enantioseparated at the multimilligram level on Chiralpak IA. Differently, Chiralpak IC was less versatile toward the considered class of compounds and only five bipyridines out of nine could be efficiently separated. In particular, on these columns, the ternary mixture n-heptane/THF/DCM (90:5:5) as MP had a positive effect on enantioseparation. An interesting phenomenon of reversal of the EEO depending on the composition of the MP for the 3,3-dibromo-5,5-bis-(E)-phenylethenyl-4,4-bipyridine along with an exceptional enantioseparation for the 3,3-dibromo-5,5-bis-ferrocenylethynyl-4,4-bipyridine (α = 8.33, R(s) = 30.6) were observed on Chiralpak IC.

Sulfur-incorporating cyclotriveratrylene analogues: the synthesis of cyclotrithioguaiacylene.

Cyclotriguaiacylene 1 is the universal precursor of cryptophanes, and represents an important intermediate for the preparation of functionalized cavitands of the cyclotriveratrylene family. Its thio analogue (cyclotrithioguaiacylene 3) was synthesized by two different routes, involving either the Newman-Kwart or the Pummerer rearrangement. The latter, performed starting from a trisulfoxide precursor, produced a purer compound in higher overall yield.