Nonconventional Luminophores: Emission Mechanism, Regulation, and Applications DOI
Zihao Zhao, Anze Li, Wang Zhang Yuan

et al.

Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 7, 2025

ConspectusNonconventional luminophores, characterized by the absence of extended (hetero)aromatic building blocks and alternating single-double/triple bonds, are composed primarily electron-rich moieties, such as heteroatoms, double aliphatic amines, carbonyls, hydroxyls, cyano groups, amides, their grouped functionalities. These unique structural features, coupled with intriguing luminescent properties, have garnered significant interest for both fundamental research promising applications, thus enabling widespread exploration. They generally benefit from abundant resources, simple synthesis, outstanding biocompatibility, excellent photostability, empowering potential applications in bioimaging, data storage encryption, anticounterfeiting, bio- chemosensing, etc. However, is preliminary, luminescence mechanisms remain elusive. For diverse systems, proposed conjectures, including tertiary amine oxidation, proton transfer, impurities, hydrogen bonding, peptide bond electron delocalization, lack consistent correlation universality, some being subsequently invalidated. This a unifying framework has hampered development effective guidelines molecular design photoluminescence (PL) regulation. To address these issues, clustering-triggered emission (CTE) mechanism, focusing on electron-molecule-aggregate multilevel structure-activity relationships, been proposed. Specifically, it identifies "clustered chromophores" moieties emissive species. The CTE mechanism not only elucidates behaviors nonconventional luminophores but also guides PL regulation further novel multifunctional materials.This Account begins concise introduction to highlighting significance delocalization (through-space conjugation) within groups. It then delves into insights gained various identifying three core components mechanism: clustering, conformational rigidity resulting clusters. proves be rational universally applicable, encompassing natural products, (macro)biomolecules, synthetic compounds extending singlet fluorescence triplet phosphorescence. By strategically coordinating elements, feasible modulate intra/intermolecular interactions, through-space conjugation, spin-orbit coupling clusters, achieving red/near-infrared (NIR) room-temperature phosphorescence (RTP) systems through internal/chemical (e.g., incorporating additional bridging units heavy atoms) external/physical pressurization, conformation adjustments) methods. Furthermore, we investigate integration emitters other conventional functional groups or substrates realize tunable photophysical properties controlling clustering states. approach leads new materials exhibiting synergistic merits high efficiency, film-forming ability, excitation- time-dependent afterglows, photochromic arising subtle rearrangement crystals. information storage, fibers, bioimaging explored. Finally, concludes forward-looking perspective challenges future luminophores.

Language: Английский

Emission Tuning of Nonconventional Luminescent Materials via Cluster Engineering DOI Open Access

Yangyang Wang,

Zuoan Liu,

Jinsong Huang

et al.

Small, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 27, 2025

Abstract Nonconventional Luminescent Materials (NLMs) with distinctive optical properties are garnering significant attention. A key challenge in their practical application lies precisely controlling emission behavior, particularly achieving excitation wavelength‐independent emission, which is paramount for accurate chemical sensing. In this study, NLMs (Y1, Y2, Y3, and Y4) synthesized via a click reaction, it found that wavelength‐dependent correlates molecular cluster formation. Rigid Y2) exhibit excitation‐independent dilute solutions nanoscale clusters but become excitation‐dependent at higher concentrations due to larger Flexible (Y3 always show indicating tendency While these high photoluminescence quantum yields (PLQYs) (0.1 mg mL −1 ) up 38.0%, they suffer from aggregation‐caused quenching (ACQ) the solid state (as low as 0.5%). These findings provide insights into NLM luminescence mechanisms offer new approach tuning properties. With excellent properties, facile synthesis, biocompatibility, hold promise bioimaging other applications.

Language: Английский

Citations

3
Nonconventional Luminophores: Emission Mechanism, Regulation, and Applications DOI
Zihao Zhao, Anze Li, Wang Zhang Yuan

et al.

Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 7, 2025

ConspectusNonconventional luminophores, characterized by the absence of extended (hetero)aromatic building blocks and alternating single-double/triple bonds, are composed primarily electron-rich moieties, such as heteroatoms, double aliphatic amines, carbonyls, hydroxyls, cyano groups, amides, their grouped functionalities. These unique structural features, coupled with intriguing luminescent properties, have garnered significant interest for both fundamental research promising applications, thus enabling widespread exploration. They generally benefit from abundant resources, simple synthesis, outstanding biocompatibility, excellent photostability, empowering potential applications in bioimaging, data storage encryption, anticounterfeiting, bio- chemosensing, etc. However, is preliminary, luminescence mechanisms remain elusive. For diverse systems, proposed conjectures, including tertiary amine oxidation, proton transfer, impurities, hydrogen bonding, peptide bond electron delocalization, lack consistent correlation universality, some being subsequently invalidated. This a unifying framework has hampered development effective guidelines molecular design photoluminescence (PL) regulation. To address these issues, clustering-triggered emission (CTE) mechanism, focusing on electron-molecule-aggregate multilevel structure-activity relationships, been proposed. Specifically, it identifies "clustered chromophores" moieties emissive species. The CTE mechanism not only elucidates behaviors nonconventional luminophores but also guides PL regulation further novel multifunctional materials.This Account begins concise introduction to highlighting significance delocalization (through-space conjugation) within groups. It then delves into insights gained various identifying three core components mechanism: clustering, conformational rigidity resulting clusters. proves be rational universally applicable, encompassing natural products, (macro)biomolecules, synthetic compounds extending singlet fluorescence triplet phosphorescence. By strategically coordinating elements, feasible modulate intra/intermolecular interactions, through-space conjugation, spin-orbit coupling clusters, achieving red/near-infrared (NIR) room-temperature phosphorescence (RTP) systems through internal/chemical (e.g., incorporating additional bridging units heavy atoms) external/physical pressurization, conformation adjustments) methods. Furthermore, we investigate integration emitters other conventional functional groups or substrates realize tunable photophysical properties controlling clustering states. approach leads new materials exhibiting synergistic merits high efficiency, film-forming ability, excitation- time-dependent afterglows, photochromic arising subtle rearrangement crystals. information storage, fibers, bioimaging explored. Finally, concludes forward-looking perspective challenges future luminophores.

Language: Английский

Citations

2