Volume 2, Issue 2 p. 72-80
Article

Fluorescence Spectroscopy of AdamBODIPY Single Crystals

Dr. Yuan-Yuan Liao

Corresponding Author

Dr. Yuan-Yuan Liao

Laboratoire PPSM ENS Cachan, CNRS, UMR 8531 & Institut d'Alembert IFR 121, 61, avenue du Président Wilson, 94235 Cachan CEDEX, France

LIONS/NIMBE, CEA-CNRS, UMR 3685, Université Paris-Saclay, 91191 Gif-sur-Yvette CEDEX, France

These authors contributed equally.

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Dr. Sigismund T.A.G. Melissen

Dr. Sigismund T.A.G. Melissen

Université de Lyon, Université Claude Bernard Lyon 1, École Normale Supérieure de Lyon, CNRS, 46 allée d'Italie, 69007 Lyon CEDEX, France

These authors contributed equally.

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Jean-Frédéric Audibert

Jean-Frédéric Audibert

Laboratoire PPSM ENS Cachan, CNRS, UMR 8531 & Institut d'Alembert IFR 121, 61, avenue du Président Wilson, 94235 Cachan CEDEX, France

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Dr. Thanh-Truc Vu

Dr. Thanh-Truc Vu

Laboratoire PPSM ENS Cachan, CNRS, UMR 8531 & Institut d'Alembert IFR 121, 61, avenue du Président Wilson, 94235 Cachan CEDEX, France

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Dr. Gilles Clavier

Dr. Gilles Clavier

Laboratoire PPSM ENS Cachan, CNRS, UMR 8531 & Institut d'Alembert IFR 121, 61, avenue du Président Wilson, 94235 Cachan CEDEX, France

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Prof. Rachel Méallet-Renault

Prof. Rachel Méallet-Renault

Laboratoire PPSM ENS Cachan, CNRS, UMR 8531 & Institut d'Alembert IFR 121, 61, avenue du Président Wilson, 94235 Cachan CEDEX, France

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Dr. Pascal Retailleau

Dr. Pascal Retailleau

Centre de Recherche de Gif, Institut de Chimie des Substances Naturelles, CNRS, UPR 2301 Bâtiment 18, 1 avenue de la Terrasse, 91198 Gif-sur-Yvette CEDEX, France

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Prof. Jean-Pierre Lemaistre

Prof. Jean-Pierre Lemaistre

Laboratoire des Milieux Désordonnés et Hétérogènes, CNRS, UMR 7603, Université P. et M. Curie, Tour 22 4, Place Jussieu, 75252 Paris CEDEX 05, France

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Prof. Valérie Génot

Prof. Valérie Génot

Laboratoire PPSM ENS Cachan, CNRS, UMR 8531 & Institut d'Alembert IFR 121, 61, avenue du Président Wilson, 94235 Cachan CEDEX, France

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Dr. Robert Pansu

Dr. Robert Pansu

Laboratoire PPSM ENS Cachan, CNRS, UMR 8531 & Institut d'Alembert IFR 121, 61, avenue du Président Wilson, 94235 Cachan CEDEX, France

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First published: 24 November 2017
Citations: 4

AdamBODIPY=adamantyl-mesityl boron dipyrromethene.

Graphical Abstract

Crystal clear: Computational investigations and time-resolved fluorescence spectroscopy were combined to study the optical properties of a single crystal of the bright organic dye AdamBODIPY. This combination of techniques enabled a determination of the intermolecular coupling energy and provided insight into the mechanism of the exciton delocalization within the crystal structure.

Abstract

Interest in the fluorescence of organic solids is increasing with the development of nanosensors and research into new molecules with aggregation-induced fluorescence properties. We have gone beyond the qualitative observation of fluorescence by analyzing the luminescence properties of planar single crystals of a 4,4′-difluoro-4-bora-(3a,4a)-diaza-s-indacene (BODIPY) derivative with micrometric dimensions. A simple Frenkel exciton model applied to this crystal predicts one band. From time-resolved fluorescence spectra, three emissions were distinguished. The shortest-lived one at λ=547 nm was predicted by theory and corresponds to an exciton lifetime of 0.9 ns. A trap with an intermediate emission lifetime of 1.2 ns was found at 569 nm and a final trap at 620 nm has a lifetime of 1.9 ns. These attributions were confirmed by the study of the polarization of these emissions. The 547 nm emission was polarized along the long axis of the crystal as predicted by the Frenkel exciton model. The 569 nm emission was polarized perpendicularly to the plane of the crystal and the 620 nm emission was polarized along the short axis. Thus, the two red-shifted bands were related to well-defined defects with specific orientations in the crystal. Fluorescence lifetime imaging measurements showed that the density of these defects is not uniform and that under our synthesis conditions, they are formed in the initial steps of the growth and therefore appear in the center of the crystals.

Conflict of interest

The authors declare no conflict of interest.