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

Garci, Amine; Abid, Seifallah; David, Arthur H. G.; Codesal, Marcos D; Đorđević, Luka; Young, Ryan M.; Sai, Hiroaki; le_bras, laura; pineau, aurelie perrier; Ovalle, Marco; Brown, Paige J; Stern, Charlotte L.; Campaña, Araceli G.; Stupp, Samuel I.; Wasielewski, Michael R.; blancos, victor; Stoddart, Fraser

doi:10.1002/ange.202208679

Cited by 4 publications

(1 citation statement)

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“…Energy transfer processes have been observed in a nonsymmetrical cyclophane 31 and in supramolecular systems 26a,32 derived from extended cyclophanes. Photon up-conversion has been detected 33 in inclusion complexes of diverse tetracationic cyclophanes and porphyrin guests, while (i) aggregation-induced emission and circularly polarized luminescence have been described 34 in chiral tetracationic boxes and (ii) exciplex photoluminescence has been identified 26b,c in homo[2]catenanes. The consequence of the nanoconfinement 35 of chromophores capable of producing 36 FRET and the dynamics of the energy transfer processes in these bischromophoric highly charged homo[2]catenanes remains, however, underexplored and is fundamentally necessary for the future use of MIMs as organic materials.…”

Section: ■ Introductionmentioning

confidence: 99%

Exciplex Emission and Förster Resonance Energy Transfer in Polycyclic Aromatic Hydrocarbon-Based Bischromophoric Cyclophanes and Homo[2]catenanes

Garci,

Abid,

David

et al. 2023

J. Am. Chem. Soc.

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Energy transfer and exciplex emission are not only crucial photophysical processes in many living organisms but also important for the development of smart photonic materials. We report, herein, the rationally designed synthesis and characterization of two highly charged bischromophoric homo[2]catenanes and one cyclophane incorporating a combination of polycyclic aromatic hydrocarbons, i.e., anthracene, pyrene, and perylene, which are intrinsically capable of supporting energy transfer and exciplex formation. The possible coconformations of the homo[2]catenanes, on account of their dynamic behavior, have been probed by Density Functional Theory calculations. The unique photophysical properties of these exotic molecules have been explored by steady-state and timeresolved absorption and fluorescence spectroscopies. The tetracationic pyrene−perylene cyclophane system exhibits emission emanating from a highly efficient Forster resonance energy transfer (FRET) mechanism which occurs in 48 ps, while the octacationic homo[2]catenane displays a weak exciplex photoluminescence following extremely fast (<0.3 ps) exciplex formation. The in-depth fundamental understanding of these photophysical processes involved in the fluorescence of bischromophoric cyclophanes and homo[2]catenanes paves the way for their use in future bioapplications and photonic devices.

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Section: ■ Introductionmentioning

confidence: 99%

Exciplex Emission and Förster Resonance Energy Transfer in Polycyclic Aromatic Hydrocarbon-Based Bischromophoric Cyclophanes and Homo[2]catenanes

Garci,

Abid,

David

et al. 2023

J. Am. Chem. Soc.

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Multifaceted regulation of chiroptical properties and self‐assembly behaviors of chiral fluorescent polymers

He,

Zhang,

et al. 2024

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The multifaceted regulation of the chiroptical properties and self‐assembly behaviors of chiral fluorescent polymers is of great significance yet remains challenging to achieve. Herein, a series of novel salen‐based chiral fluorescent polymers with aggregation‐induced emission and varied substitution manners were facilely and efficiently synthesized. Multiple factors were systematically investigated on the chiroptical properties and self‐assembly performance of these polymers, which include molecular structures, solvent environments, metal coordination, and liquid crystal (LC) assemblies. Sutle change in the solvent composition can lead to diverse assembly morphologies of all these chiral polymers, from single‐handed helical fibers, helical toroids or loops, to spherical structures, consequently leading to an aggregation‐reduced circular dichroism (CD) phenomenon. The polymers bearing salen units show highly selective and reversible coordination with Zn2+ and can also induce multiple responses in the absorption, luminescence, CD, and circularly polarized luminescence (CPL) of these chiral fluorescent polymers via a coordination‐ and dissociation‐initiated self‐assembly tuning. Furthermore, a small amount of the chiral fluorescent polymer in can induce achiral nematic 4‐cyano‐4′‐n‐pentylbiphenyl (5CB) to form ordered chiral nematic LC phase with significant improvement in their CD and CPL signal. The absolute absorption and luminescent dissymmetry factors of the resulting supramolecular assemblies can reach the order of 10−1.

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Unraveling the Origin of Multichannel Circularly Polarized Luminescence in a Pyrene‐Functionalized Topologically Chiral [2]Catenane

Wang,

Wu,

Wang

et al. 2024

Angewandte Chemie

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Mechanically interlocked molecules (MIMs) are promising platform for developing functionalized artificial molecular machines. The construction of chiral MIMs with appealing circularly polarized luminescence (CPL) properties has boosted their potential application in biomedicine and optical industry. However, there is currently little knowledge about the CPL emission mechanism as well as the emission dynamics of these related MIMs. Herein, we demonstrate that time‐resolved circularly polarized luminescence (TRCPL) spectroscopy combined with transient absorption (TA) spectroscopy offers a feasible approach to elucidate the origins of CPL emission in pyrene‐functionalized topologically chiral [2]catenane as well as in a series of pyrene‐functionalized chiral molecules. For the first time, direct evidence differentiating the chiroptical signals originating from either topological (local state emission) or Euclidean chirality (excimer state emission) in these pyrene‐functionalized chiral molecules has been discovered. Our work not only establishes a novel and ideal methodology to study CPL mechanism, but also provides a theoretical foundation for the rational design of novel chiral materials in the future.

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

Cited by 4 publications

References 93 publications

Exciplex Emission and Förster Resonance Energy Transfer in Polycyclic Aromatic Hydrocarbon-Based Bischromophoric Cyclophanes and Homo[2]catenanes

Exciplex Emission and Förster Resonance Energy Transfer in Polycyclic Aromatic Hydrocarbon-Based Bischromophoric Cyclophanes and Homo[2]catenanes

Multifaceted regulation of chiroptical properties and self‐assembly behaviors of chiral fluorescent polymers

Unraveling the Origin of Multichannel Circularly Polarized Luminescence in a Pyrene‐Functionalized Topologically Chiral [2]Catenane

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