Aggregation-Induced Emission and Circularly Polarized Luminescence Duality in Tetracationic Binaphthyl-Based Cyclophanes

Amine Garci; Seifallah Abid; Arthur H G David; Marcos D Codesal; Luka Đorđević; Ryan M Young; Hiroaki Sai; Laura Le Bras; Aurélie Perrier; Marco Ovalle; Paige J Brown; Charlotte L Stern; Araceli G Campaña; Samuel I Stupp; Michael R Wasielewski; Victor Blanco; J Fraser Stoddart

doi:10.1002/anie.202208679

Aggregation-Induced Emission and Circularly Polarized Luminescence Duality in Tetracationic Binaphthyl-Based Cyclophanes

Angew Chem Int Ed Engl. 2022 Oct 4;61(40):e202208679. doi: 10.1002/anie.202208679. Epub 2022 Aug 22.

Authors

Amine Garci¹, Seifallah Abid¹, Arthur H G David¹, Marcos D Codesal², Luka Đorđević^{1

3}, Ryan M Young^{1

4}, Hiroaki Sai^{1

5

6}, Laura Le Bras⁷, Aurélie Perrier^{8

9}, Marco Ovalle¹, Paige J Brown^{1

4}, Charlotte L Stern¹, Araceli G Campaña², Samuel I Stupp^{1

3

5

6

10

11}, Michael R Wasielewski^{1

4}, Victor Blanco², J Fraser Stoddart^{1

12

13

14}

Affiliations

¹ Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208, USA.
² Departamento de Química Orgánica, Facultad de Ciencias, Unidad de Excelencia de Química Aplicada a Biomedicina y Medioambiente (UEQ), Universidad de Granada (UGR), Avda. Fuente Nueva S/N, 18071, Granada, Spain.
³ Center for Bio-inspired Energy Science, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208, USA.
⁴ Institute for Sustainability and Energy at Northwestern, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208, USA.
⁵ Simpson Querrey Institute for BioNanotechnology, Northwestern University, 303 E. Superior Street, Chicago, IL 60611, USA.
⁶ Department of Materials Science and Engineering, Northwestern University, 2220 Campus Drive, Evanston, IL 60208, USA.
⁷ Laboratoire Chrono-environnement (UMR 6249), Université de Bourgogne Franche-Comté, 16 route de Gray, 25030, Besançon, France.
⁸ Chimie Paris Tech, PSL Research University, CNRS, Institute of Chemistry for Life and Health Sciences (i-CLeHS), UMR 8060, 75005, Paris, France.
⁹ Université Paris Cité, 75006, Paris, France.
¹⁰ Department of Biomedical Engineering, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208, USA.
¹¹ Department of Medicine, Northwestern University, 676N St. Clair Street, Chicago, IL 60611, USA.
¹² School of Chemistry, University of New South Wales, Sydney, NSW 2052, Australia.
¹³ Stoddart Institute of Molecular Science, Department of Chemistry, Zhejiang University, Hangzhou, 310027, China.
¹⁴ ZJU-Hangzhou Global Scientific and Technological Innovation Center, Hangzhou, 311215, China.

Abstract

Here, we report an approach to the synthesis of highly charged enantiopure cyclophanes by the insertion of axially chiral enantiomeric binaphthyl fluorophores into the constitutions of pyridinium-based macrocycles. Remarkably, these fluorescent tetracationic cyclophanes exhibit a significant AIE compared to their neutral optically active binaphthyl precursors. A combination of theoretical calculations and time-resolved spectroscopy reveal that the AIE originates from limited torsional vibrations associated with the axes of chirality present in the chiral enantiomeric binaphthyl units and the fine-tuning of their electronic landscape when incorporated within the cyclophane structure. Furthermore, these highly charged enantiopure cyclophanes display CPL responses both in solution and in the aggregated state. This unique duality of AIE and CPL in these tetracationic cyclophanes is destined to be of major importance in future development of photonic devices and bio-applications.

Keywords: Aggregation-Induced Emission; Chirality; Circularly Polarized Luminescence; Macrocycles; Optoelectronics.

Publication types

Research Support, Non-U.S. Gov't
Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

Fluorescent Dyes / chemistry
Luminescence*
Luminescent Measurements* / methods
Stereoisomerism

Substances

Fluorescent Dyes