TY - JOUR
T1 - Bent-core liquid crystalline cyanostilbenes
T2 - fluorescence switching and thermochromism
AU - Martínez-Abadía, M.
AU - Varghese, Shinto
AU - Milián-Medina, B.
AU - Gierschner, J.
AU - Giménez, R.
AU - Ros, M.B.
N1 - The authors from ICMA greatly appreciate financial support from the Spanish Government (MINECO-FEDER project MAT2012-38538-C03-01), the Aragon's Government and FSE (project E04) and the Jae PreDoc-CSIC (M. M.-A.) fellowship program.
PY - 2015/5/7
Y1 - 2015/5/7
N2 - Fluorescent bent-core molecules, bearing one or two cyanostilbene units in the lateral structure and different positions of the cyano group (α- or β-isomers), are described with the aim of modulating the molecular packing and fluorescence properties. These compounds give rise to a variety of crystal polymorphs and bent-core liquid crystalline phases (SmCP, Colr and B6), offering the unique chance to study the fluorescence properties of the cyanostilbene structure in different phases. Experimental and computational studies elucidate geometrical and electronic properties of these bent-core structures but especially the fluorescence properties (spectral positions, quantum yields and decay curves), in a detailed comparison between diluted solutions, in dichloromethane (DCM) or poly(methylmethacrylate) (PMMA), and condensed phases. Quantum yields as high as 70% have been obtained in some diluted solutions (PMMA) and condensed phases. Remarkably, the quantum yield values depend on the position of the cyano group, being higher for β- than for the α-isomers due to the higher radiative rates and lower non-radiative rates of the former. The photophysical characterization in the condensed phase focuses on RT studies with solid samples and different processing, and show that, upon aggregation, interactions between the cyanostilbene groups result in changes of the emission spectra and dynamics compared to the diluted systems in DCM and PMMA, giving rise to H-aggregations of varying strength. Furthermore, the compounds exhibit thermochromism, showing a green-yellow fluorescence in the pristine crystalline phase that changes to blue on heating to the liquid crystal phase. This journal is
AB - Fluorescent bent-core molecules, bearing one or two cyanostilbene units in the lateral structure and different positions of the cyano group (α- or β-isomers), are described with the aim of modulating the molecular packing and fluorescence properties. These compounds give rise to a variety of crystal polymorphs and bent-core liquid crystalline phases (SmCP, Colr and B6), offering the unique chance to study the fluorescence properties of the cyanostilbene structure in different phases. Experimental and computational studies elucidate geometrical and electronic properties of these bent-core structures but especially the fluorescence properties (spectral positions, quantum yields and decay curves), in a detailed comparison between diluted solutions, in dichloromethane (DCM) or poly(methylmethacrylate) (PMMA), and condensed phases. Quantum yields as high as 70% have been obtained in some diluted solutions (PMMA) and condensed phases. Remarkably, the quantum yield values depend on the position of the cyano group, being higher for β- than for the α-isomers due to the higher radiative rates and lower non-radiative rates of the former. The photophysical characterization in the condensed phase focuses on RT studies with solid samples and different processing, and show that, upon aggregation, interactions between the cyanostilbene groups result in changes of the emission spectra and dynamics compared to the diluted systems in DCM and PMMA, giving rise to H-aggregations of varying strength. Furthermore, the compounds exhibit thermochromism, showing a green-yellow fluorescence in the pristine crystalline phase that changes to blue on heating to the liquid crystal phase. This journal is
UR - http://www.rsc.org/suppdata/c5/cp/c5cp00696a/c5cp00696a1.pdf
U2 - 10.1039/c5cp00696a
DO - 10.1039/c5cp00696a
M3 - Article
AN - SCOPUS:84928555557
SN - 1463-9076
VL - 17
SP - 11715
EP - 11724
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
IS - 17
ER -