Exciton Delocalization Counteracts the Energy Gap: A New Pathway toward NIR-Emissive Dyes DOI Creative Commons
Alexei Cravcenco, Yi Yu, Fredrik Edhborg

et al.

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(45), P. 19232 - 19239

Published: Nov. 8, 2021

Exciton coupling between the transition dipole moments of ordered dyes in supramolecular assemblies, so-called J/H-aggregates, leads to shifted electronic transitions. This can lower excited state energy, allowing for emission well into near-infrared regime. However, as we show here, it is not only energy modifications that J-aggregates provide. A bay-alkylated quaterrylene was synthesized, which found form 1,1,2,2-tetrachloroethane. combination superradiance and a decreased nonradiative relaxation rate made J-aggregate four times more emissive than monomeric counterpart. reduced nonintuitive consequence following 180 nm (3300 cm–1) red-shift comparison absorption. gap law, commonly invoked rationalize increased rates with increasing wavelength, also contains reorganization term. The highly suppressed due exciton delocalization, framework law could therefore reproduce our experimental observations. J-Aggregates thus circumvent common belief lowering energies results large are pathway toward organic NIR

Language: Английский

Slip‐Stacked J‐Aggregate Materials for Organic Solar Cells and Photodetectors DOI
Jin Hong Kim,

Tim Schembri,

David Bialas

et al.

Advanced Materials, Journal Year: 2021, Volume and Issue: 34(22)

Published: Oct. 19, 2021

Abstract Dye–dye interactions affect the optical and electronic properties in organic semiconductor films of light harvesting detecting optoelectronic applications. This review elaborates how to tailor these semiconductors for solar cells (OSCs) photodiodes (OPDs). While devices rely on similar materials, demands their are rather different, former requiring a broad absorption spectrum spanning from UV over visible up near‐infrared region latter an ultra‐narrow at specific, targeted wavelength. In order design satisfying demands, fundamental insights relationship provided depending molecular packing arrangement resultant coupling thereof. Based recent advancements theoretical understanding intermolecular between slip‐stacked dyes, distinguishing classical J‐aggregates with predominant long‐range Coulomb charge transfer (CT)‐mediated or ‐coupled J‐aggregates, whose red‐shifts primarily governed by short‐range orbital interactions, is suggested. Within this framework, aggregate structure functional representative classes dye aggregates analyzed most advanced OSCs wavelength‐selective OPDs, providing important into rational thin‐film materials.

Language: Английский

Citations

149

Progress and Perspective of Solid-State Organic Fluorophores for Biomedical Applications DOI
Ke Li, Tian‐Bing Ren, Shuangyan Huan

et al.

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(50), P. 21143 - 21160

Published: Dec. 8, 2021

Fluorescent organic dyes have been extensively used as raw materials for the development of versatile imaging tools in field biomedicine. Particularly, solid-state fluorophores (SSOFs) past 20 years has exhibited an upward trend. In recent years, studies on SSOFs focused advanced tools, such optical contrast agents and phototherapy agents, biomedical applications. However, practical application these hindered owing to several limitations. Thus, this Perspective, we provided insights that could aid researchers further develop overcome limitations limited aqueous dispersibility, low biocompatibility, uncontrolled emission. First, described inherent photophysical properties fluorescence mechanisms conventional, aggregation-induced emissive, precipitating with respect their Subsequently, highlighted functionalized bioimaging, biosensing, theranostics. Finally, elucidated potential prospects current SSOF-based associated

Language: Английский

Citations

109

Molecular Carbon Imides DOI
Wei Jiang, Zhaohui Wang

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(33), P. 14976 - 14991

Published: July 29, 2022

The creation and development of new forms nanocarbons have fundamentally transformed the scientific landscape in past three decades. As members nanocarbon family with accurate size, shape, edge structure, molecular carbon imides (MCIs) shown unexpected unique properties. Particularly, imide functionalization strategy has endowed these rylene-based carbons fascinating characteristics involving flexible syntheses, tailor-made structures, diverse properties, excellent processability, good stability. This Perspective elaborates design evolution to functional landscapes, illustrative examples are given, including a promising library multi-size multi-dimensional MCIs rigidly conjugated π-architectures, ranging from 1D nanoribbon 2D nanographene cross-dimensional MCIs. Although researchers achieved substantial progress using as components for exploration charge transport, photoelectric conversion, chiral luminescence performances, they far unleashing their full potential. Developing highly efficient regioselective coupling/ring-closure reactions formation multiple C–C bonds annulation electron-deficient aromatic units is crucial. Prediction by theory help machine learning artificial intelligence research along reliable nanotechnology characterization will give an impetus blossom related fields. Future investigations also advance toward─or even focus on─the emerging potential functions, especially fields electronics spin electronics, which expected open avenues.

Language: Английский

Citations

106

Accelerating symmetry-breaking charge separation in a perylenediimide trimer through a vibronically coherent dimer intermediate DOI
Chenjian Lin, Taeyeon Kim, Jonathan D. Schultz

et al.

Nature Chemistry, Journal Year: 2022, Volume and Issue: 14(7), P. 786 - 793

Published: April 25, 2022

Language: Английский

Citations

100

Molecular-level enhanced clusterization-triggered emission of nonconventional luminophores in dilute aqueous solution DOI Creative Commons
Qiuju Li, Xingyi Wang,

Qi-Su Huang

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Jan. 25, 2023

Abstract Nonconjugated and nonaromatic luminophores based on clustering-triggered emission derived from through-space conjugation have drawn emerging attention in recent years. The reported nonconventional are emissive concentrated solution and/or the solid state, but they tend to be nonluminescent dilute solution, which greatly limits their sensing imaging applications. Herein, we design unique clusteroluminogens through modification of cyclodextrin (CD) with amino acids enable intermolecular intramolecular clusterization chromophores CD-based confined space. resulted interactions along conformation rigidification originated hydrogen bond interaction complexation generate blue cyan fluorescence even (0.035 wt.%, quantum yield 40.70%). Moreover, prepared histidine-modified CD (CDHis) is demonstrated for fluorescent detection chlortetracycline high sensitivity selectivity. This work provides a new universal strategy synthesize bright aqueous molecular-level enhanced clusterization-triggered emission.

Language: Английский

Citations

69

In situ orderly self-assembly strategy affording NIR-II-J-aggregates for in vivo imaging and surgical navigation DOI Creative Commons
Zhe Li,

Ping‐Zhao Liang,

Li Xu

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: April 3, 2023

Abstract J-aggregation, an effective strategy to extend wavelength, has been considered as a promising method for constructing NIR-II fluorophores. However, due weak intermolecular interactions, conventional J-aggregates are easily decomposed into monomers in the biological environment. Although adding external carriers could help stabilize, such methods still suffer from high-concentration dependence and unsuitable activatable probes design. Besides, these carriers-assisted nanoparticles risky of disassembly lipophilic Herein, by fusing precipitated dye (HPQ) which orderly self-assembly structure, onto simple hemi-cyanine conjugated system, we construct series activatable, high-stability NIR-II-J-aggregates overcome carrier’s situ vivo. Further, employ probe HPQ-Zzh-B achieve long-term imaging tumor precise resection navigation reducing lung metastasis. We believe this will advance development controllable bioimaging

Language: Английский

Citations

54

Anomalous deep-red luminescence of perylene black analogues with strong π-π interactions DOI Creative Commons
Ningning Tang, Jiadong Zhou, Liangxuan Wang

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: April 6, 2023

Abstract Perylene bisimide (PBI) dyes are known as red, maroon and black pigments, whose colors depend on the close π−π stacking arrangement. However, contrary to luminescent monomers, deep-red PBI pigments commonly non- or only weakly fluorescent due (multiple) quenching pathways. Here, we introduce N -alkoxybenzyl substituted PBIs that contain π arrangement (exhibiting d ≈ 3.5 Å, longitudinal transversal displacements of 3.1 Å 1.3 Å); however, they afford emitters with solid-state fluorescence quantum yields ( Φ F ) up 60%. Systematic photophysical computational studies in solution solid state reveal a sensitive interconversion PBI-centred locally excited charge transfer state, which depends dihedral angle θ between benzyl alkoxy groups. This effectively controls emission process, enables high by circumventing common pathways observed for perylene analogues.

Language: Английский

Citations

47

Comprehensive analysis of dye adsorption and supramolecular interaction between dyes and cotton fibers in non-aqueous media/less water dyeing system DOI
Liujun Pei,

He Zhu,

Siping Gong

et al.

Industrial Crops and Products, Journal Year: 2024, Volume and Issue: 222, P. 119955 - 119955

Published: Nov. 4, 2024

Language: Английский

Citations

21

Symmetry-Breaking Charge Separation and Null Aggregates DOI
Frank C. Spano

The Journal of Physical Chemistry C, Journal Year: 2024, Volume and Issue: 128(1), P. 248 - 260

Published: Jan. 2, 2024

The relationship between symmetry-breaking charge separation (SB-CS) and null aggregate (NA) formation in molecular dimer complexes is investigated theoretically, with applications mainly to dimers based on PDI chromophores. Both processes derive from points, which are defined by degeneracies either the upper or lower adiabatic exciton bands. Hamiltonian contains intermolecular coupling derived interacting transition dipole moments (Coulomb coupling), gives rise Frenkel excitons, as well excitons charge-transfer (CT) driven electron (te) hole (th) hopping integrals. A recipe for efficient SB-CS presented, which, beyond Weller condition─which holds that solvent-stabilized CT state should appear below optical gap -includes two additional conditions: presence of a point and, just important, lopsided transfer integrals, |te| ≫ |th| |te|. When such conditions met, developing asymmetry optimized response small fluctuations polar solvent-induced electric field, eventually leads charge-separated state. It shown can also occur H-dimers significant cofacial overlap, consistent observations made several groups.

Language: Английский

Citations

18

Chirality of Perylene Diimides: Design Strategies and Applications DOI
Jie Li, Pengyu Li, Mingyu Fan

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(27)

Published: March 31, 2022

Abstract Chirality is a particularly important concept in nature and exists at all length scales, ranging from the molecular level to supramolecular level. Over last two decades, various design strategies have been developed construct chiral materials based on perylene diimides (PDIs) mimic assembly process biological systems, but applications of these aggregates are still an early stage. This Minireview summarizes recent progress synthesis properties PDIs. The chirality PDI‐based can be generated by three different approaches: twisted planes PDIs, substituents co‐assembly achiral PDIs guests. A comprehensive understanding as well potential future developments also provided.

Language: Английский

Citations

66