A Calix[3]acridan‐Based Host–Guest Cocrystal Exhibiting Efficient Thermally Activated Delayed Fluorescence

Zhou, He‐Ye; Zhang, Dawei; Li, Meng; Chen, Chuan‐Feng

doi:10.1002/ange.202117872

Cited by 17 publications

(3 citation statements)

References 61 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The confinement of guest molecule 1 amplifies the intersystem crossing (ISC) and the charge transfer process. 46 As a result, the fluorescence signal vanishes, and a red-shifted phosphorescence emission emerges relative to PTS{1′} and PTS{1}. Despite modulating the excitation wavelength, their phosphorescent emission peaks remain predominant (Figure S29).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Different from the cocrystals PTS{1} and PTS{1′} , the use of cage templating G + and K + cations results in the formation of “pyrene box” molecular cages. The confinement of guest molecule 1 amplifies the intersystem crossing (ISC) and the charge transfer process . As a result, the fluorescence signal vanishes, and a red-shifted phosphorescence emission emerges relative to PTS{1′} and PTS{1} .…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Modulation of Deep-Red to Near-Infrared Room-Temperature Charge-Transfer Phosphorescence of Crystalline “Pyrene Box” Cages by Coupled Ion/Guest Structural Self-Assembly

Feng,

Chen,

Zhao

et al. 2024

J. Am. Chem. Soc.

View full text Add to dashboard Cite

Organic cocrystals obtained from multicomponent self-assembly have garnered considerable attention due to their distinct phosphorescence properties and broad applications. Yet, there have been limited reports on cocrystal systems that showcase efficient deep-red to near-infrared (NIR) charge-transfer (CT) phosphorescence. Furthermore, effective strategies to modulate the emission pathways of both fluorescence and phosphorescence remain underexplored. In this work, we dedicated our work to four distinct self-assembled cocrystals called “pyrene box” cages using 1,3,6,8-pyrenetetrasulfonate anions (PTS 4– ), 4-iodoaniline (1), guanidinium (G + ), diaminoguanidinium (A 2 G + ), and hydrated K + countercations. The binding of such cations to PTS 4– platforms adaptively modulates their supramolecular stacking self-assembly with guest molecules 1, allowing to steer the fluorescence and phosphorescence pathways. Notably, the confinement of guest molecule 1 within “pyrene box” PTSK{1} and PTSG{1} cages leads to an efficient deep-red to NIR CT phosphorescence emission. The addition of fuming gases like triethylamine and HCl allows reversible pH modulations of guest binding, which in turn induce a reversible transition of the “pyrene box” cage between fluorescence and phosphorescence states. This capability was further illustrated through a proof-of-concept demonstration in shrimp freshness detection. Our findings not only lay a foundation for future supramolecular designs leveraging weak intermolecular host–guest interactions to engineer excited states in interacting chromophores but also broaden the prospective applications of room-temperature phosphorescence materials in food safety detection.

show abstract

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Modulation of Deep-Red to Near-Infrared Room-Temperature Charge-Transfer Phosphorescence of Crystalline “Pyrene Box” Cages by Coupled Ion/Guest Structural Self-Assembly

Feng,

Chen,

Zhao

et al. 2024

J. Am. Chem. Soc.

View full text Add to dashboard Cite

show abstract

“…Novel and functional macrocyclic hosts with conformational change and cavity tunability have sparked a lot of interest in molecular recognition and supramolecular materials. − They also serve as promising building blocks in the design of coordination supramolecular architectures with rich host–guest chemistry. − Recently, we have reported a flexible organopalladium host built from a dynamic macrocyclic ligand with two m -methylphenyl linkers, which exhibited both induced-fit guest binding and efficient photooxidation catalysis.…”

Section: Introductionmentioning

confidence: 99%

Dynamic Interconversion and Induced-Fit Guest Binding with Two Macrocycle-Based Coordination Cages

Xia

Zhong

et al. 2023

Inorg. Chem.

View full text Add to dashboard Cite

We report the syntheses and host–guest chemistry of two interconvertible coordination cages, Pd2L2 and Pd1L1, from a dynamic macrocycle ligand (L) and a cis-blocking (tmen)Pd(NO3)2 (tmen = tetramethylethylenediamine) unit (Pd). The water-soluble macrocyclic L, which can bind various polycyclic aromatic hydrocarbon (PAH) guests in its cis-conformation, was constructed via four pyridinium bonds between two 2,4,6-tri(4-pyridyl)-1,3,5-triazine [TPT] panels and two p-xylene bridges. We selectively formed each cage either by changing the reaction concentration/solvent/temperature or through induced-fit guest encapsulation, while direct assembly of L and Pd resulted in a mixture of Pd2L2 and Pd1L1 in equilibrium. X-ray structures of the free ligand and the host–guest complexes confirmed the induce-fit adaptive changes in the ligand’s conformation and the cage’s cavity. This work demonstrates a useful strategy for designing multistimuli-responsive supramolecular hosts by coordination self-assembly with macrocyclic ligands featuring rich conformational freedom.

show abstract

Long‐Lived Emissive Hydrogen‐Bonded Macrocycles: Donors Regulating Room‐Temperature Phosphorescence and Thermally Activated Delayed Fluorescence

Lian

Yang

et al. 2023

Advanced Optical Materials

View full text Add to dashboard Cite

Despite vast applications of macrocycles in supramolecular chemistry, achieving long‐lived emissions including room‐temperature phosphorescence (RTP) or thermally activated delayed fluorescence (TADF) for potential use still presents a great challenge. This work first reports hydrogen‐bonded (H‐bonded) macrocycles emitting RTP and TADF by introducing various donors onto the same aramide skeleton containing a rigid acceptor. The formation of charge transfer effectively enhances the photoluminescence efficiency. Aromatic carbonyl groups promote the intersystem crossing. The drastically reduced flexibility of chromophores fixed by the H‐bonded macrocyclic framework contributes to suppress the nonradiative decay to stabilize triplet excitons. Therefore, RTP and TADF are acquired by altering donors, and are systematically revealed by comparisons with control compounds and theoretical calculations. Finally, near white‐light emission (CIE, 0.30, 0.33) is realized via host–guest interactions.

show abstract

A Calix[3]acridan‐Based Host–Guest Cocrystal Exhibiting Efficient Thermally Activated Delayed Fluorescence

Cited by 17 publications

References 61 publications

Modulation of Deep-Red to Near-Infrared Room-Temperature Charge-Transfer Phosphorescence of Crystalline “Pyrene Box” Cages by Coupled Ion/Guest Structural Self-Assembly

Modulation of Deep-Red to Near-Infrared Room-Temperature Charge-Transfer Phosphorescence of Crystalline “Pyrene Box” Cages by Coupled Ion/Guest Structural Self-Assembly

Dynamic Interconversion and Induced-Fit Guest Binding with Two Macrocycle-Based Coordination Cages

Long‐Lived Emissive Hydrogen‐Bonded Macrocycles: Donors Regulating Room‐Temperature Phosphorescence and Thermally Activated Delayed Fluorescence

Contact Info

Product

Resources

About