Very intense polarized emission in self-assembled room temperature metallomesogens based on Zn(ii) coordination complexes: an experimental and computational study

Autor: Elisabeta I. Szerb, Emilie Voirin, Otilia Costisor, Bertrand Donnio, Mario Amati, Benoît Heinrich, Massimo La Deda, Valentin Badea, Angela Candreva, Giuseppe Di Maio, Evelyn Popa, Adelina A. Andelescu
Přispěvatelé: Donnio, Bertrand, Università della Calabria [Arcavacata di Rende] (Unical), Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Romanian Academy, Politehnica University of Timisoara (UPT), Università degli studi della Basilicata [Potenza] (UNIBAS)
Rok vydání: 2022
Předmět:
[CHIM.INOR] Chemical Sciences/Inorganic chemistry
[PHYS.PHYS.PHYS-OPTICS] Physics [physics]/Physics [physics]/Optics [physics.optics]
[PHYS.PHYS.PHYS-OPTICS]Physics [physics]/Physics [physics]/Optics [physics.optics]
Quenching (fluorescence)
Materials science
[CHIM.ORGA]Chemical Sciences/Organic chemistry
Transition dipole moment
Quantum yield
Mesophase
General Chemistry
Time-dependent density functional theory
[CHIM.COOR] Chemical Sciences/Coordination chemistry
[CHIM.INOR]Chemical Sciences/Inorganic chemistry
[CHIM.ORGA] Chemical Sciences/Organic chemistry
Crystallography
chemistry.chemical_compound
chemistry
Excited state
[CHIM.CRIS]Chemical Sciences/Cristallography
Materials Chemistry
Molecule
[CHIM.COOR]Chemical Sciences/Coordination chemistry
[CHIM.CRIS] Chemical Sciences/Cristallography
Terpyridine
Zdroj: Journal of Materials Chemistry C
Journal of Materials Chemistry C, 2021, 10 (1), pp.115-125. ⟨10.1039/d1tc05059a⟩
ISSN: 2050-7534
2050-7526
Popis: International audience; Three room-temperature metallomesogens based on Zn(II) cations pentacoordinated by different chelating N^N^N terpyridines and two monodentate gallate co-ligands were designed and synthesized. Depending on the terpyridine ligand's tip functionality, the complexes self-assemble into either a 3D hexagonal mesophase or into a columnar hexagonal mesophase. A systematic study between the structure (molecular architecture, arrangement of the molecules and columns, and chains in both types of mesophases) and photophysical properties (emission maxima and yields, lifetimes of the excited states in the mesophase), correlated with investigations of single molecules in solution, was conducted. Remarkably, one complex exhibited a record quantum yield of 95.0% in solution, while in the mesophase, despite quenching due to the radiative deactivation from the ILCT state, still retained a considerable emission yield of ϕ = 20.2%. The polarized emission of an oriented film, determined for the first time in columnar metallomesogens, shows a dichroic emission ratio (I||/I⊥) of 1.30. DFT and TDDFT computational studies confirmed the origin of the observed fluorescence anisotropy from the transition dipole moment oriented along the C2 symmetry axis of the molecule combined with a high level of order in the 3D mesophase.
Databáze: OpenAIRE
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