Utilizing “Latent” Carbon: Repositioning Hydrogen‐Bonded Synthons and Assemblies via Halogen Bonding to π‐Systems DOI Creative Commons
Jogirdas Vainauskas, Alexander Wahrhaftig‐Lewis, Tomislav Friščić

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(37)

Published: May 23, 2024

Abstract Molecules bearing carboxylic acid, amide, and hydroxyl groups are ubiquitous in crystal engineering, where robust hydrogen‐bonded synthons centred on these functionalities enable reliable structure design. We now show that halogen bonding to the carbon π‐system of such molecules, traditionally ignored permits recognition directional assembly resulting structural subunits, leaving archetypal ring, ladder, chain homosynthons intact, but repositioned space. When applied heteromolecular synthons, this enables rearranging more complex motifs evolution binary cocrystals into ternary ones through “latent” carbon‐based sites, demonstrating a rational approach build higher‐order solid‐state supramolecular assemblies.

Language: Английский

Achieving High‐Temperature Phosphorescence by Organic Cocrystal Engineering DOI
Manjeet Singh,

Kang Shen,

Wenpeng Ye

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(14)

Published: Feb. 7, 2024

Abstract Organic phosphors offer a promising alternative in optoelectronics, but their temperature‐sensitive feature has restricted applications high‐temperature scenarios, and the attainment of phosphorescence (HTP) is still challenging. Herein, series organic cocrystal are constructed by supramolecular assembly with an ultralong emission lifetime up to 2.16 s. Intriguingly, remarkable stabilization triplet excitons can also be realized at elevated temperature, green exhibited solid state even 150 °C. From special molecular packing within crystal lattice, it been observed that orientation isolated water cluster well‐controlled organization via multiple interactions favor structural rigidity cocrystals more effectively suppress nonradiative transition, thus resulting efficient room‐temperature unprecedented survival HTP.

Language: Английский

Citations

33
Photofunctional cyclophane host–guest systems DOI
Swadhin Garain, Frank Würthner

Chemical Communications, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

This feature article presents cyclophane-based host–guest complexes for which electronic interactions between the host and guest molecules can modulate excited-state properties in an advanced way involving both singlet triplet excited states.

Language: Английский

Citations

2
Role of Halobenzene Guest Molecules in Modulating Room Temperature Phosphorescence of Benzophenone–Naphthalene Diimide Inclusion Crystals DOI

Yoshifumi Tsukiyama,

Yusei Yamamoto,

D. Koga

et al.

Chemistry - An Asian Journal, Journal Year: 2024, Volume and Issue: 19(5)

Published: Feb. 7, 2024

Materials exhibiting room temperature phosphorescence (RTP) have recently emerged as a subject of significant interest. In this study, we successfully created inclusion crystals by introducing halobenzenes guests into host molecule combining benzophenone with naphthalene diimide. This approach led to the creation fascinating fluorescence and RTP properties dependent on guest molecules. Notably, containing chlorobenzene showed cyan fluorescence, while those iodobenzene displayed red RTP. difference highlights impact luminescent properties, external heavy-atom effect playing key role in promoting efficient intersystem crossing between excited singlet triplet states. Crystals bromobenzene exhibited unique blend RTP, both from diimide, highlighting moderate effect. These findings reveal composite materials remarkably diverse interesting optical characteristics.

Language: Английский

Citations

5
Wide-range tunable circularly polarized luminescence in triphenylamine supramolecular polymers via charge-transfer complexation DOI Creative Commons
Yuchen Guo, Yifei Zhang,

Jianfei Ma

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Oct. 28, 2024

Circularly polarized luminescence materials with broad color tunability are highly valuable for applications in 3D display and photonic technologies. Here we show that incorporating intermolecular charge-transfer complexation into chiral supramolecular polymers is an efficient strategy to achieve this objective. Adjusting the strength between triphenylamine donors naphthalenemonoimide acceptors enables tunable circularly signals across visible light spectrum. This includes blue-colored emission donor polymers, as well green, yellow, orange red-colored donor-acceptor polymers. The packing modes further influenced by presence or absence of acetylene linkages on donors, resulting ground- excited-state charge transfer varying luminescent lifetimes. Additionally, white-light achieved encapsulating blue- orange-emitting species surfactant-based micelles a compartmentalized manner. Overall, manipulating provides effective approach wide-range materials.

Language: Английский

Citations

5
Ultralong thermally activated delayed fluorescence based on intermolecular charge transfer induced by isomer in carbazole derivative DOI Creative Commons
Junru Chen, Xianhe Zhang,

Zongliang Xie

et al.

Aggregate, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 2, 2024

Abstract Ultralong thermally activated delayed fluorescence (UTADF) materials play an important role in realizing time‐dependent color‐tunable afterglow. Some typical carbazole (Cz) derivatives have been reported to exhibit UTADF properties. However, a 10‐fold difference TADF lifetime was found between commercial Cz and the corresponding lab‐synthesized ones, which indicated that may not be derived from single as reported. To reveal real mechanism, we synthesized three one isomer form host‐guest pairs for optical studies. The photophysical properties revealed originated intermolecular charge transfer host guest, while ultralong organic phosphorescence guest. Thanks rich color variations luminescence displayed by 4‐(1H‐benzo[f]indol‐1‐yl)−4′‐(9H‐carbazol‐9‐yl)‐[1,1′‐biphenyl]−3,3′‐dicarbonitrile/4,4′‐di(9H‐carbazol‐9‐yl)‐[1,1′‐biphenyl]−3,3′‐dicarbonitrile (CBP‐2CN) at different delay times, it can applied realize multi‐dimensional encryption both time luminescent color.

Language: Английский

Citations

4
Molecular engineering charge transfer and triplet exciton formation in donor–acceptor cocrystals DOI
Malik L. Williams, Jonathan R. Palmer, Samuel B. Tyndall

et al.

The Journal of Chemical Physics, Journal Year: 2025, Volume and Issue: 162(2)

Published: Jan. 9, 2025

Organic donor–acceptor (D–A) cocrystals are gaining attention for their potential applications in optoelectronic devices. This study explores the dynamics of charge transfer (CT) and triplet exciton formation various D–A cocrystals. By examining a series composed coronene (COR), peri-xanthenoxanthene (PXX), perylene (PER) donors paired with N,N-bis(3′-pentyl)perylene-3,4:9,10-bis(dicarboximide) (PDI), naphthalene-1,4:5,8-tetracarboxy-dianhydride (NDA), or pyrene-4,5,9,10-tetraone (PTO) acceptors, using transient absorption microscopy time-resolved electron paramagnetic resonance spectroscopy, we find that strength CT interaction influences nature yield excitons produced by state recombination. In particular, PER-PDI, COR-PTO, PER-PTO cocrystals, localized lower energy than state. contrast, no available to states PXX-NDA, PER-NDA, PXX-PTO as result, rapidly decay ground formation. Moreover, density functional theory calculations show transition between delocalized single donor acceptor unit provides source spin–orbit coupling necessary when energetically accessible. These findings provide insights into design molecular materials tailored properties applications.

Language: Английский

Citations

0
Bottom‐Up Selective Growth of Ultralong Organic Phosphorescence Nanocrystals with Optimized Crystal Forms for In Vivo Optical Imaging DOI Open Access
Junru Chen,

Zhen-Ni Wei,

Yi Shan

et al.

Advanced Materials, Journal Year: 2025, Volume and Issue: unknown

Published: March 24, 2025

Ultralong organic phosphorescence (UOP) materials are valuable for biological imaging to avoid interference from fluorescence background signals because of their delayed emission property. Obtaining nanocrystals with high quantum yield is a critical factor achieve high-quality UOP imaging. Herein, pair host-guest doped system variable crystal forms the host constructed. By exploring relationship between form and system, importance revealed in systems. Furthermore, overcome low crystallinity numerous defects faced by traditional bottom-up strategies nanocrystal preparation, strategy proposed selective preparation target form. Through controlling evaporation rate solvent, ordered growth crystals can be effectively regulated obtain different bioimaging applications.

Language: Английский

Citations

0
Core-Substituted Pyromellitic Diimides: A Versatile Molecular Scaffold for Tunable Triplet Emission DOI
Sopan M. Wagalgave,

Anju Ajayan Kongasseri,

U.P. Singh

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 28, 2025

Arylene diimides represent a versatile class of n-type organic semiconductors, widely recognized for tunable photophysical properties, making them highly relevant across various optoelectronic applications. While their fluorescence can be finely modulated through core substitution, triplet-state emission has received comparatively little attention. This is particularly surprising given the growing field ambient-organic triplet harvesting materials, such as thermally activated delayed and phosphorescent systems, which would greatly benefit from structural modifications to π-conjugated backbone substitution arylene achieve desired properties. Realizing states within family molecules crucial advancing triplet-based materials applications in lighting, photocatalysis, beyond. In this context, we present an unprecedented study demonstrating pyromellitic diimides, smallest member diimide family, with accessible emissive state due narrow singlet-triplet energy gap. Herein, report synthesis series core-substituted (cPmDIs) using diverse synthetic strategies. Core not only induces wide spectrum colors but, notably, enables wide-range phosphorescence spanning visible spectrum, depending on substituent. article details electrochemical characterization library cPmDIs, supported by theory. Furthermore, demonstrate potential molecular design achieving ambient-orange phosphorescence, exemplified thiophenyl-cPmDI derivative, exhibits crystalline film minimizing vibrational dissipation. regard, envision that represents significant step toward predictive structure-property phosphors materials.

Language: Английский

Citations

0
Dynamic photo-enhanced polyacrylic acid-based room temperature phosphorescence materials with persistent long-wavelength and even near-infrared luminescence via Förster resonance energy transfer DOI

Liuqi Kong,

Shaochen Sun,

Yan Zhu

et al.

Dyes and Pigments, Journal Year: 2024, Volume and Issue: 226, P. 112131 - 112131

Published: March 30, 2024

Language: Английский

Citations

3
Multicolor Room-Temperature Phosphorescence Achieved by Intrinsic Polymers Containing Solely One Phosphor Unit DOI

Jiayue Huang,

Lunjun Qu, Liang Gao

et al.

Macromolecules, Journal Year: 2024, Volume and Issue: 57(10), P. 5018 - 5027

Published: May 10, 2024

Room-temperature phosphorescence (RTP) materials have attracted much attention due to their unique luminescence properties. However, it is very challenging tune the afterglow color of pure amorphous polymers by using only one kind phosphor unit so far. Here, we proposed a strategy induce pyrene derivatives (VPY) into main chain polymer free radical copolymerization, followed alcoholysis form poly(vinyl alcohol) derivative (PVA–PVPY) with strong hydrogen bond network structures. It was surprising that obtained intrinsic containing achieved multicolor long-lived RTP. The RTP performance exhibited concentration, excitation, and time dependence. experimental theoretical results demonstrated these characteristics were attributed different aggregated states units in chains, which revealed mechanism isolated produce In addition, explored application based on color-tunable properties information encryption flexible wearables. This contributes development multicolored smart luminescent as well wearable materials.

Language: Английский

Citations

3