Divinylanthracene-Containing Tetracationic Organic Cyclophane with Near-Infrared Photoluminescence

David, Arthur H. G.; Garci, Amine; Abid, Seifallah; Li, Xuesong; Young, Ryan M.; Seale, James S W; Hornick, Jessica E.; Azad, Chandra S.; Jiao, Yang; Roy, Indranil; Akpınar, Işıl; Kesharwani, Tanay; Stern, Charlotte L.; Wasielewski, Michael R.

doi:10.1021/jacs.3c01244

Cited by 8 publications

(2 citation statements)

References 93 publications

(41 reference statements)

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“…Researchers have successfully prepared cyclic compounds with various structural types such as ladder-like, ring-like, cage-like, and dendritic ( Figure 1 ) [ 17 , 18 , 19 , 20 , 21 ]. When these cyclic compounds form cyclic radicals through electronic oxidation, the open-shell compounds exhibit unique magnetic, optical, and electronic properties that can be used to construct paramagnetic reagents and magnetic materials [ 22 , 23 , 24 , 25 , 26 , 27 ]. Due to the introduction of nitrogen atoms, nitrogen-containing heterocyclic compounds have relatively low oxidation potentials, and the substitution of methylene by nitrogen atoms strengthens the redox activity [ 28 ].…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Properties of Novel Alkyl-Substituted Hexaazacyclophanes and Their Diradical Dications

Li,

Chen

2024

Molecules

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Radicals based on arylamine cyclophanes can be used as functional materials and show application potential in fields such as synthetic chemistry, molecular electronic components, organic light-emitting diodes, and catalytic chemistry. Using a Buchwald–Hartwig palladium-catalyzed aryl halide amination method, we synthesized a series of neutral hexaazacyclophane compounds 1–3 with different substituents in the meta–meta–meta positions of the phenyl rings. Three characteristic high-spin hexaazacyclophane diradical dications were obtained by two-electron oxidation using AgSbF6: 12·+•2[SbF6]−, 22·+•2[SbF6]−, and 32·+•2[SbF6]−. The electronic structures and physical properties of these compounds were then investigated by 1H and 13C nuclear magnetic resonance spectroscopy, cyclic voltammetry, electron paramagnetic resonance spectroscopy, superconducting quantum interferometry, ultraviolet–visible spectroscopy, and density functional theory calculations. The findings provide new ideas for designing radical species with novel physical properties and electronic structures. Importantly, the obtained radical species are not sensitive to air, making them valuable functional materials for practical applications.

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Section: Introductionmentioning

confidence: 99%

Synthesis and Properties of Novel Alkyl-Substituted Hexaazacyclophanes and Their Diradical Dications

Li,

Chen

2024

Molecules

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“…In this context, investigations of pyridinium-based extended tetracationic cyclophanes and their octacationic homo[2]catenane counterparts, including chromophores and PAHs, are essential since these highly charged compounds are among the well-defined molecules that have attracted interest on account of their potential for inclusion in host–guest systems, efficient photocatalysts, , bioimaging agents, , and even in single-molecule electronics . Furthermore, the photophysical properties of these types of compounds are of major interest.…”

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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Reversible Redox‐Driven Crystallization in a Paracyclophane Monolayer at a Solid–Liquid Interface

Li,

Mali,

Hapiot

et al. 2024

Adv Funct Materials

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The development and integration of cyclophanes into future functional materials require a detailed understanding of the physicochemical principles that underlie their properties, phase behavior, and in particular the relationship between structure and function. Here, electrochemically switchable crystallization of a ferrocene‐bearing 3D Janus tecton (M‐Fc) at the interface between highly oriented pyrolytic graphite (HOPG) and an electrolyte solution is demonstrated. The M‐Fc adlayer is successfully visualized under both ambient and electrochemical conditions using scanning tunneling microscopy. Voltammetric measurements show a surface‐confined redox process for the M‐Fc modified surface that drives the phase transition between a visible 2D ordered linear phase (M‐Fc0, with ferrocene in the neutral state) and an invisible gas‐like adsorption layer with high mobility when ferrocene is oxidized, M‐Fc+, and a “square scheme” mechanism explains the data. Analogous experiments in a ferrocene‐free tecton adlayer show no phase transition and confirm that the dynamics in M‐Fc are redox‐driven. On‐surface 3D nanoarchitectures are also demonstrated by forming inclusion complexes between M‐Fc and β‐cyclodextrin and device behavior through electrochemical scanning tunneling spectroscopy (STS). These results showcase the functional potential of this class of cyclophanes, which can find use in actuators, optical crystals, and other smart materials.

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Divinylanthracene-Containing Tetracationic Organic Cyclophane with Near-Infrared Photoluminescence

Cited by 8 publications

References 93 publications

Synthesis and Properties of Novel Alkyl-Substituted Hexaazacyclophanes and Their Diradical Dications

Synthesis and Properties of Novel Alkyl-Substituted Hexaazacyclophanes and Their Diradical Dications

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

Reversible Redox‐Driven Crystallization in a Paracyclophane Monolayer at a Solid–Liquid Interface

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