Organic Chemistry

"N2O2" Metal-azaDIPY complexes: a new class of NIR-fluorophores

Authors

  • Amélie Godard Institut de Chimie Moléculaire de l’Université de Bourgogne, Université Bourgogne Franche-Comté, CNRS UMR 6302, Dijon, France ,
  • Laura Abad Galan Univ Lyon, Ecole Normale Supérieure de Lyon, CNRS, Laboratoire de Chimie, UMR 5182, F-69342 Lyon, France ,
  • Jean Rouillon Univ Lyon, Ecole Normale Supérieure de Lyon, CNRS, Laboratoire de Chimie, UMR 5182, F-69342 Lyon, France ,
  • Shaymaa Al Shehimy Univ Lyon, Ecole Normale Supérieure de Lyon, CNRS, Laboratoire de Chimie, UMR 5182, F-69342 Lyon, France ,
  • Wassima Tajani Institut de Chimie Moléculaire de l’Université de Bourgogne, Université Bourgogne Franche-Comté, CNRS UMR 6302, Dijon, France ,
  • Charlotte Cave Institut de Chimie Moléculaire de l’Université de Bourgogne, Université Bourgogne Franche-Comté, CNRS UMR 6302, Dijon, France ,
  • Raluca Malacea-Kabbara Institut de Chimie Moléculaire de l’Université de Bourgogne, Université Bourgogne Franche-Comté, CNRS UMR 6302, Dijon, France ,
  • Yoann Rousselin Institut de Chimie Moléculaire de l’Université de Bourgogne, Université Bourgogne Franche-Comté, CNRS UMR 6302, Dijon, France ,
  • Pierre Le Gendre Institut de Chimie Moléculaire de l’Université de Bourgogne, Université Bourgogne Franche-Comté, CNRS UMR 6302, Dijon, France ,
  • Arnaud Fihey Univ Rennes, CNRS, ISCR (Institut des Sciences Chimiques de Rennes)−UMR 6226, F-35000 Rennes, France ,
  • Mohamed Bendellaa Univ. Grenoble Alpes, Institute for Advanced Biosciences, Inserm U 1209 / CNRS 5309, 38000 Grenoble, France ,
  • Benoit Busser Univ. Grenoble Alpes, Institute for Advanced Biosciences, Inserm U 1209 / CNRS 5309, 38000 Grenoble, France & Institut Universitaire de France (IUF), France & Department of Clinical biochemistry, Grenoble Alpes University Hospital, 38043 Grenoble, France ,
  • Lucie Sancey Univ. Grenoble Alpes, Institute for Advanced Biosciences, Inserm U 1209 / CNRS 5309, 38000 Grenoble, France ,
  • Boris Le Guennic Univ Rennes, CNRS, ISCR (Institut des Sciences Chimiques de Rennes)−UMR 6226, F-35000 Rennes, France ,
  • Christophe Bucher Univ Lyon, Ecole Normale Supérieure de Lyon, CNRS, Laboratoire de Chimie, UMR 5182, F-69342 Lyon, France ,
  • Olivier Maury Univ Lyon, Ecole Normale Supérieure de Lyon, CNRS, Laboratoire de Chimie, UMR 5182, F-69342 Lyon, France. ,
  • Christine Goze Institut de Chimie Moléculaire de l’Université de Bourgogne, Université Bourgogne Franche-Comté, CNRS UMR 6302, Dijon, France ,
  • Ewen Bodio Institut de Chimie Moléculaire de l’Université de Bourgogne, Université Bourgogne Franche-Comté, CNRS UMR 6302, Dijon, France

Abstract

Aza-BODIPYs are an increasingly studied class of fluorophores. They can be seen as an "aza-DIPY" ligand rigidified by a metalloid, a boron atom. Based on this idea, a series of complexes of group 13 metals (aluminum and gallium) have been synthesized and characterized. Impact of the metal and of the nature of the substituents of aza-DIPY core were investigated. The photophysical and electrochemical properties were determined and an X-ray structure of an azaGaDIPY was obtained. These data reveal that azaGaDIPY and azaAlDIPY exhibit significant red-shifted fluorescence compared to their analogue aza-BODIPY. Their emission can go up to 800 nm for the maximum emission length and up to NIR-II for the emission tail. This, associated with their electrochemical stability (no metal release whether oxidized or reduced) make them a promising class of fluorophores for optical medical imaging. Moreover, X-ray structure and molecular modeling studies have shown that this red shift seems to be more due to the geometry around the boron/metal than to the nature of the metal.

Content

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Supplementary material

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Supplementary information
Synthetic procedures; NMR, absorption, emission spectra; additionnal figures for electrochemical characterization; additionnal figure for theoretical study; X-ray structure details...