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1.
Chem Asian J ; 19(9): e202400112, 2024 May 02.
Artículo en Inglés | MEDLINE | ID: mdl-38353579

RESUMEN

An original series of bipyrimidine-based chromophores featuring alkoxystyryl donor groups bearing short chiral (S)-2-methylbutyl chains in positions 4, 3,4 and 3,5, connected to electron-accepting 2,2-bipyrimidine rings, has been developed. Their linear and non-linear optical properties were studied using a variety of techniques, including one- and two-photon absorption spectroscopy, fluorescence measurements, as well as Hyper-Rayleigh scattering to determine the first hyperpolarizabilities. Their electronic and geometrical properties were rationalized by TD-DFT calculations. The thermal properties of the compounds were also investigated by a combination of polarized light optical microscopy, differential scanning calorimetry measurements and small-angle X-ray scattering experiments. The derivatives were found not to have mesomorphic properties, but to exhibit melting temperatures or cold crystallization behavior that enabled the isolation of well-organized thin films. The nonlinear optical properties of amorphous or crystalline thin films were studied by wide-field second harmonic generation and multiphoton fluorescence imaging, confirming that non-centrosymmetric crystal organization enables strong second and third harmonic generation. This new series confirms that our strategy of functionalizing 3D organic octupoles with short chiral chains to generate non-centrosymmetric organized thin films enables the development of highly second order nonlinear optical active materials without the use of corona-poling or tedious deposition techniques.

2.
Turk J Chem ; 45(1): 71-81, 2021.
Artículo en Inglés | MEDLINE | ID: mdl-33679154

RESUMEN

Liquid crystal (LC) compound 4-Benzyloxyphenyl 4-[4-( n -dodecyloxy)benzoyloxy]benzoate (BDBB) was prepared and characterized. Inverse gas chromatography (IGC) was to be a beneficial analysis method for the research of thermodynamic characteristics of the new LC. Acetate and alcohol isomers were used to examine LC selectivity via the IGC technique at temperatures between 333.2 K and 483.2 K. The retention diagrams of n -heptane, n -octane, n -nonane, n -decane, undecane, dodecane, tridecane, n -butyl acetate, isobutyl acetate, ethyl acetate, n -propylbenzene, isopropylbenzene, ethylbenzene, chlorobenzene, and toluene on BDBB were plotted with temperatures of 483.2-493.2 K. Flory-Huggins interaction parameter and weight fraction activity coefficient at infinite dilution were researched for BDBB.

3.
Soft Matter ; 12(35): 7405-22, 2016 Sep 21.
Artículo en Inglés | MEDLINE | ID: mdl-27510177

RESUMEN

A bent-core compound derived from a 4-cyanoresorcinol core unit with two terephthalate based rod-like wings and carrying chiral 3,7-dimethyloctyloxy side chains has been synthesized in racemic and enantiomerically pure form and characterized by polarizing microscopy, differential scanning calorimetry, X-ray diffraction and electro-optical investigations to study the influence of molecular chirality on the superstructural chirality and polar order in lamellar liquid crystalline phases. Herein we demonstrate that the coupling of molecular chirality with superstructural layer chirality in SmCsPF domain phases (forming energetically distinct diastereomeric pairs) can fix the tilt direction and thus stabilize synpolar order, leading to bistable ferroelectric switching in the SmC* phases of the (S)-enantiomer, whereas tristable modes determine the switching of the racemate. Moreover, the mechanism of electric field induced molecular reorganization changes from a rotation around the molecular long axis in the racemate to a rotation on the tilt-cone for the (S)-enantiomer. At high temperature the enantiomer behaves like a rod-like molecule with a chirality induced ferroelectric SmC* phase and an electroclinic effect in the SmA'* phase. At reduced temperature sterically induced polarization, due to the bent molecular shape, becomes dominating, leading to much higher polarization values, thus providing access to high polarization ferroelectric materials with weakly bent compounds having only "weakly chiral" stereogenic units. Moreover, the field induced alignment of the SmCsPF(()*()) domains gives rise to a special kind of electroclinic effect appearing even in the absence of molecular chirality. Comparison with related compounds indicates that the strongest effects of chirality appear for weakly bent molecules with a relatively short coherence length of polar order, whereas for smectic phases with long range polar order the effects of the interlayer interfaces can override the chirality effects.

4.
Chemphyschem ; 17(10): 1425-9, 2016 05 18.
Artículo en Inglés | MEDLINE | ID: mdl-26910727

RESUMEN

We investigated the electro-optic response in the "foggy" amorphous blue phase (BPIII) as well as in the isotropic phase. To the best of our knowledge, such a study has not yet been performed due to the very limited thermal range of BPIII. In this study, we used a single-component chiral bent-core liquid crystal with a self-stabilized BPIII, which is stable over a wide temperature range. The results show that the response time is on the order of hundreds of microseconds in the isotropic phase and increases to 1-2 ms in the BPIII (at TI-BP -T <1), then drastically increases up to a few tens of milliseconds upon further cooling in BPIII. Such an unusual behavior was explained on the basis of the high rotational viscosity and/or the existence of nanoscale smectic (Sm) clusters. The Kerr constant was also measured and found to be ∼500 pm V(-2) , which is the largest among bent-core BP systems reported so far and comparable with that of polymer-stabilized BPs.

5.
Chem Commun (Camb) ; 51(35): 7512-5, 2015 May 01.
Artículo en Inglés | MEDLINE | ID: mdl-25834996

RESUMEN

4-Cyanoresorcinol derived bent-core molecules with a chiral (S)-2-methylbutoxy chain form liquid crystalline phases with TGBA- and TGBC-like structures at the transition from cybotactic nematic via SmA to SmC phases.

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