Cyano terminated tolane compounds for polymer dispersed liquid crystal application: relationship between cyano terminated tolane based molecular structures and electro-optical properties

ABSTRACT

The structures of the liquid crystal (LC) molecules have a key role in impacting the electro-optical performance of a polymer dispersed liquid crystal (PDLC) film. In this paper, the relationship between the LC molecular structures and the electro-optical properties of PDLC films is investigated based on an unexplored cyano-terminated tolane compounds (CTTCs) doped E8 LCs/UV polymers system. Due to the high polarity of CTTCs, LCs doped with the cyano-terminated tolane (CTT) molecules exhibit high birefringence and large positive dielectric anisotropy. On the whole, PDLC films doped with the CTT molecules exhibit a lower driving voltage than that doped with the pure E8. More excitingly, PDLC films based on CTT molecules with larger length-to-width ratio and longer conjugated system show higher contrast ratio (CR) and faster response time. Eventually, the mechanism of the effects of CTT-based molecular structures and the relationship between the electro-optical performance of PDLC films and CTT molecules are illustrated. This work paves a new way for optimising the electro-optical properties of PDLC films.     

Palladium‐catalyzed unstrained C(sp3)―N bond activation: the synthesis of N,N‐dimethylacetamide by carbonylation of trimethylamine

This work describes a highly efficient unstrained C(sp³)―N bond activation approach for synthesis of N,N‐dimethylacetamide (DMAc) via catalytic carbonylation of trimethylamine using a PdCl₂/bipy (bipy = 2,2′‐bipyridine)/Me₄NI catalyst system. A low Pd catalyst dosage (1.0 mol%) is sufficient for high selectivity (98.1%) and yield (90.8%), with a turnover number (TON) of 90.0 mmol of DMAc obtained per mmol of PdCl₂ employed under mild reaction conditions. The influence of reaction parameters such as catalyst precursor dosage, ligand type and promoter on activity is investigated. This work also discusses in detail the halide promoter's role in the reaction, and provides a plausible mechanism based on the intermediates methyl iodide and acetyl iodide. Analyses indicate that the carbonylation of trimethylamine may proceed through an active intermediate acetyl iodide formed by carbonylation of methyl iodide generated from the decomposition of the promoter Me₄NI under reaction conditions. The formation of acetyl iodide favors the cleaving efficiency of the inert unstrained C(sp³)―N bond of trimethylamine. Copyright © 2013 John Wiley & Sons, Ltd.     

Rhodium-Catalyzed Enantioselective Synthesis,Structures, and Properties of Single and Double Azahelicene-Like Molecules

The enantioselective synthesis of aza[6] and [7]helicene-like molecules have been achieved by the cationic rhodium(I)/axially chiral biaryl bisphosphine complex-catalyzed intramolecular [2+2+2] cycloaddition of cyanodiynes. This protocol was successfully applied to the diastereo- and enantioselective synthesis of an S-shaped double aza[6]helicene-like molecule with a high ee value of 89 %. Although no epimerization and racemization were observed in the double carbo[6]helicene-like molecule at 80 °C, epimerization and racemization of the double aza[6]helicene-like molecule proceeded at 80 °C. This double aza[6]helicene-like molecule showed good fluorescent quantum yields and chiroptical responses under both neutral and acidic conditions.     

Chiral Chromium Salen@rGO as Multipurpose and Recyclable Heterogeneous Catalyst

The first immobilization of a pyrene-tagged chromium salen complex through π-π noncovalent interactions on reduced graphene oxide (rGO) is described. A very robust supported catalytic system is obtained to promote asymmetric catalysis in repeated cycles, without loss of activity or enantioselectivity. This specific behavior was demonstrated in two different catalytic reactions (up to ten reuses) promoted by chromium salen complexes, the cyclohexene oxide ring-opening reaction and the hetero-Diels-Alder cycloaddition between various aldehydes and Danishefsky's diene. Furthermore, the chiral chromium salen@rGO has been found to be compatible with a multi-substrate type use, in which the structure of the substrate involved is modified each time the catalyst is reused.     

A Water Molecule Triggers Guest Exchange at a Mono-Zinc Centre Confined in a Biomimetic Calixarene Pocket: a Model for Understanding Ligand Stability in Zn Proteins

In this study, the ligand exchange mechanism at a biomimetic Zn^II centre, embedded in a pocket mimicking the possible constrains induced by a proteic structure, is explored. The residence time of different guest ligands (dimethylformamide, acetonitrile and ethanol) inside the cavity of a calix[6]arene-based tris(imidazole) tetrahedral zinc complex was probed using 1D EXchange SpectroscopY NMR experiments. A strong dependence of residence time on water content was observed with no exchange occurring under anhydrous conditions, even in the presence of a large excess of guest ligand. These results advocate for an associative exchange mechanism involving the transient exo-coordination of a water molecule, giving rise to 5-coordinate Zn^II intermediates, and inversion of the pyramid at the Zn^II centre. Theoretical modelling by DFT confirmed that the associative mechanism is at stake. These results are particularly relevant in the context of the understanding of kinetic stability/lability in Zn proteins and highlight the key role that a single water molecule can play in catalysing ligand exchange and controlling the lability of Zn^II in proteins.