Browse
Submit Data
Databases
API
Help

Dataset Information

20 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Modulation of circularly polarized luminescence through excited-state symmetry breaking and interbranched exciton coupling in helical push-pull organic systems.

ABSTRACT: ?-Helical push-pull dyes were prepared and their (chir)optical properties were investigated both experimentally and computationally. Specific fluorescent behaviour of bis-substituted system was observed with unprecedented solvent effect on the intensity of circularly polarized luminescence (CPL, dissymmetry factor decreasing from 10-2 to 10-3 with an increase in solvent polarity) that was linked to a change in symmetry of chiral excited state and suppression of interbranched exciton coupling. The results highlight the potential of CPL spectroscopy to study and provide a deeper understanding of electronic photophysical processes in chiral ?-conjugated molecules.

SUBMITTER: Dhbaibi K

PROVIDER: S-EPMC7069512 | biostudies-literature | 2020 Jan

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Modulation of circularly polarized luminescence through excited-state symmetry breaking and interbranched exciton coupling in helical push-pull organic systems.

Dhbaibi Kais K Favereau Ludovic L Srebro-Hooper Monika M Quinton Cassandre C Vanthuyne Nicolas N Arrico Lorenzo L Roisnel Thierry T Jamoussi Bassem B Poriel Cyril C Cabanetos Clément C Autschbach Jochen J Crassous Jeanne J

Chemical science 20191120 2

π-Helical push-pull dyes were prepared and their (chir)optical properties were investigated both experimentally and computationally. Specific fluorescent behaviour of bis-substituted system was observed with unprecedented solvent effect on the intensity of circularly polarized luminescence (CPL, dissymmetry factor decreasing from 10<sup>-2</sup> to 10<sup>-3</sup> with an increase in solvent polarity) that was linked to a change in symmetry of chiral excited state and suppression of interbranche ...[more]

PMID: 32206274

Similar Datasets

Achieving high circularly polarized luminescence with push-pull helicenic systems: from rationalized design to top-emission CP-OLED applications.

Project description:While the development of chiral molecules displaying circularly polarized luminescence (CPL) has received considerable attention, the corresponding CPL intensity, g lum, hardly exceeds 10-2 at the molecular level owing to the difficulty in optimizing the key parameters governing such a luminescence process. To address this challenge, we report here the synthesis and chiroptical properties of a new family of π-helical push-pull systems based on carbo[6]helicene, where the latter acts as either a chiral electron acceptor or a donor unit. This comprehensive experimental and theoretical investigation shows that the magnitude and relative orientation of the electric (μe ) and magnetic (μ m ) dipole transition moments can be tuned efficiently with regard to the molecular chiroptical properties, which results in high g lum values, i.e. up to 3-4 × 10-2. Our investigations revealed that the optimized mutual orientation of the electric and magnetic dipoles in the excited state is a crucial parameter to achieve intense helicene-mediated exciton coupling, which is a major contributor to the obtained strong CPL. Finally, top-emission CP-OLEDs were fabricated through vapor deposition, which afforded a promising g El of around 8 × 10-3. These results bring about further molecular design guidelines to reach high CPL intensity and offer new insights into the development of innovative CP-OLED architectures.

| S-EPMC8179576 | biostudies-literature

Excited state dynamics and exciton diffusion in triphenylamine/dicyanovinyl push-pull small molecule for organic optoelectronics.

Project description:Triphenylamine-based small push-pull molecules have recently attracted substantial research attention due to their unique optoelectronic properties. Here, we investigate the excited state de-excitation dynamics and exciton diffusion in TPA-T-DCV-Ph-F small molecule, having simple chemical structure with asymmetrical architecture and end-capped with electron-withdrawing p-fluorodicyanovinyl group. The excited state lifetime in diluted solutions (0.04 ns in toluene and 0.4 ns in chloroform) are found to be surprisingly shorter compared to the solid state (3 ns in PMMA matrix). Time-dependent density functional theory indicates that this behavior originates from non-radiative relaxation of the excited state through a conical intersection between the ground and singlet excited state potential energy surfaces. Exciton diffusion length of ~ 16 nm in solution processed films was retrieved by employing time-resolved photoluminescence volume quenching measurements with Monte Carlo simulations. As means of investigating the device performance of TPA-T-DCV-Ph-F, we manufactured solution and vacuum processed bulk heterojunction solar cells that yielded efficiencies of ~ 1.5% and ~ 3.7%, respectively. Our findings demonstrate that the short lifetime in solutions does not hinder per se long exciton diffusion length in films thereby granting applications of TPA-T-DCV-Ph-F and similar push-pull molecules in vacuum and solution processable devices.

| S-EPMC7713310 | biostudies-literature

Exciton coupling in diketopyrrolopyrrole-helicene derivatives leads to red and near-infrared circularly polarized luminescence.

Project description:Molecular and macromolecular chiral ?-conjugated diketopyrrolopyrrole (DPP)-helicene derivatives were prepared and their chiroptical properties examined experimentally and theoretically. Exciton coupling leads to red and near-infrared circularly polarized absorption and luminescence arising from the achiral DPP units in the helical environment, highlighting an interesting synergy between the chiral helicene and the organic dye.

| S-EPMC5872492 | biostudies-literature

A [2]Rotaxane-Based Circularly Polarized Luminescence Switch.

Project description:A rotaxane-based molecular shuttle has been synthesized in which the switching of the position of a fluorescent macrocycle on the thread turns "on" or "off" the circularly polarized luminescence (CPL) of the system while maintaining similar fluorescence profiles and quantum yields in both states. The chiroptical activity relies on the chiral information transfer from an ammonium salt incorporating d- or l-phenylalanine residues as chiral stereogenic covalent units to an otherwise achiral crown ether macrocycle bearing a luminescent 2,2'-bipyrene unit when they interact through hydrogen bonding. Each enantiomeric thread induces CPL responses of opposite signs on the macrocycle. Upon addition of base, the switching of the position of the macrocycle to a triazolium group disables the chiral information transfer to the macrocycle, switching "off" the CPL response. The in situ switching upon several acid/base cycles is also demonstrated.

| S-EPMC6975276 | biostudies-literature

Circularly polarized luminescence from organic micro-/nano-structures.

Project description:Circularly polarized light exhibits promising applications in future displays and photonic technologies. Circularly polarized luminescence (CPL) from chiral luminophores is an ideal approach to directly generating circularly polarized light, in which the energy loss induced by the circularly polarized filters can be reduced. Among various chiral luminophores, organic micro-/nano-structures have attracted increasing attention owing to the high quantum efficiency and luminescence dissymmetry factor. Herein, the recent progress of CPL from organic micro-/nano-structures is summarized. Firstly, the design principles of CPL-active organic micro-/nano-structures are expounded from the construction of micro-/nano-structure and the introduction of chirality. Based on these design principles, several typical organic micro-/nano-structures with CPL activity are introduced in detail, including self-assembly of small molecules, self-assembly of π-conjugated polymers, and self-assembly on micro-/nanoscale architectures. Subsequently, we discuss the external stimuli that can regulate CPL performance, including solvents, pH value, metal ions, mechanical force, and temperature. We also summarize the applications of CPL-active materials in organic light-emitting diodes, optical information processing, and chemical and biological sensing. Finally, the current challenges and prospects in this emerging field are presented. It is expected that this review will provide a guide for the design of excellent CPL-active materials.

| S-EPMC8039044 | biostudies-literature

Water-soluble chiral tetrazine derivatives: towards the application of circularly polarized luminescence from upper-excited states to photodynamic therapy.

Project description:A new family of water-soluble chiral tetrazine derivatives 1 and 2 is reported. Spectroscopic studies reveal that the derivatives violate Kasha's rule and emit from their upper-excited states (S n , n > 1). The transition assignments are supported by time-dependent density functional theory calculations. More importantly, both chromophores exhibit anisotropy factors on the order of ∼10-3 to 10-4 for circular dichroism and circularly polarized luminescence (CPL) from upper-excited states. Additionally, the nonplanar geometry of the derivatives induces a significant yield of triplet excited states. Transient absorption spectroscopic measurements reveal high triplet quantum yields of ∼86% for 1 and ∼81% for 2. Through in vitro studies, we demonstrate that the derivatives can be used as photodynamic therapy (PDT) agents, providing a highly efficient form of cancer therapy. This study is the first demonstration of simple organic molecules with CPL from upper-excited states and efficient PDT.

| S-EPMC6471655 | biostudies-literature

Sequentially amplified circularly polarized ultraviolet luminescence for enantioselective photopolymerization.

Project description:Chiral optical materials based on circularly polarized luminescence (CPL) have emerged rapidly due to their feasible applications in diverse fields of research. However, limited to the small luminescence dissymmetry factor (glum), real application examples have rarely been reported. Here, we present a complex system, which show intense circularly polarized ultraviolet luminescence (CPUVL) with large glum value, enabling a chiral UV light triggered enantioselective polymerization. By integrating sensitized triplet-triplet annihilation upconversion and CPL, both visible-to-UV upconversion emission and upconverted circularly polarized ultraviolet luminescence (UC-CPUVL) were obtained in the systems, built of chiral annihilator R(S)-4,12-biphenyl[2,2]paracyclophane (R-/S-TP), and a thermally activated delayed fluorescence (TADF) sensitizer. After dispersing this upconversion system into room-temperature nematic liquid crystal, induced chiral nematic liquid crystal could significantly amplify the glum value (0.19) of UC-CPUVL. Further, the UC-CPUVL emission has been used to trigger the enantioselective photopolymerization of diacetylene. This work paves the way for the further development of functional application of CPL active materials.

| S-EPMC7652877 | biostudies-literature

Chiral Diketopyrrolopyrrole-Helicene Polymer With Efficient Red Circularly Polarized Luminescence.

Project description:Chiral diketopyrrolopyrrole (DPP)-helicene polymers were synthesized to develop efficient red circularly polarized (CP) light emitters. These original chiral dyes display intense electronic circular dichroism (ECD) and CP luminescence (CPL) in the far-red spectral region owing to the presence of excitonic coupling between achiral DPPs within the chiral environment of the polymeric structure. This work affords an interesting example illustrating the potential of π-conjugated helical polymers for chiral optoelectronic applications.

| S-EPMC7160364 | biostudies-literature

A chemosensor-based chiral coassembly with switchable circularly polarized luminescence.

Project description:Fluorescent chemosensors represent fast response to analytes with pronounced luminescent variations. They are promising as potential candidates in controlling luminescence and chiroptical activities of self-assembled chiral systems, which however have not been accomplished to date. We present a coassembled multiple component system that could respond to SO2 derivatives, giving rise to dynamic aggregation behaviors and switchable luminescence as well as circularly polarized luminescence (CPL). Cholesteryl-naphthalimide and coumarin derivatives coassemble into vesicles and nanohelices under the solvent strategy, behaving as energy transfer donor and accepter respectively. Energy transfer enables CPL transition from green to red depending on the molar fraction. After the addition of SO2 derivatives, hypochromic shifts occur to CPL due to the nucleophilic addition reaction to coumarin domain, hindering energy transfer and allow for the emergence of pristine luminescence. Here, we show a protocol to control over luminescence and chiroptical features of supramolecular chiral self-assemblies using fluorescent chemosensors.

| S-EPMC8566482 | biostudies-literature

Solvent tuning of photochemistry upon excited-state symmetry breaking.

Project description:The nature of the electronic excited state of many symmetric multibranched donor-acceptor molecules varies from delocalized/multipolar to localized/dipolar depending on the environment. Solvent-driven localization breaks the symmetry and traps the exciton in one branch. Using a combination of ultrafast spectroscopies, we investigate how such excited-state symmetry breaking affects the photochemical reactivity of quadrupolar and octupolar A-(?-D)2,3 molecules with photoisomerizable A-?-D branches. Excited-state symmetry breaking is identified by monitoring several spectroscopic signatures of the multipolar delocalized exciton, including the S2???S1 electronic transition, whose energy reflects interbranch coupling. It occurs in all but nonpolar solvents. In polar media, it is rapidly followed by an alkyne-allene isomerization of the excited branch. In nonpolar solvents, slow and reversible isomerization corresponding to chemically-driven symmetry breaking, is observed. These findings reveal that the photoreactivity of large conjugated molecules can be tuned by controlling the localization of the excitation.

| S-EPMC7174366 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data