Non‐alternant Benzodifluoranthene Tetraimides from 7,8,9,10‐Fluoranthene Diimides: Synthesis, Structure, and Optical‐Limiting Properties DOI

Hanwen Qin,

Lingli Zhao,

Liping Zheng

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 30, 2024

A novel tetraimide-functionalized non-alternant π-conjugated system, namely, benzodifluoranthene tetraimides (BDFTI), has been designed and synthesized through highly efficient UV-photocyclization of a vinyl-bridged fluoranthene diimide dimer (i. e., FDI-V). The synthesis FDI-V starts from straightforward three-step route to produce 7,8,9,10-fluoranthene (FDIs) building-blocks, followed by nearly complete bromination then Stille-coupling reaction give the desired dimer. analysis X-ray crystallography confirms near-coplanar geometry for FDIs, while BDFTI shows U-shaped distorted backbone configuration proven theoretical optimizations. tetraimide exhibits several advantages over FDI cores, including an extended absorption band red-shift in photoluminescence spectra. This enhancement can be attributed presence additional electron-deficient imide units, which promotes increased intramolecular charge transfer improved electron affinity. All imides show local aromatic characteristic owing incorporation pentagon rings π-frameworks. fully fused nonlinear optical properties as analyzed open-aperture Z-scan technique, demonstrating superior optical-limiting performance compared FDI-V. versatile chemistries provide pathway developing complex unique multiimide-functionalized systems, paving way creating high-performance materials.

Language: Английский

Spin-Correlated Luminescence of a Carbazole-Containing Diradical Emitter: Single-Molecule Magnetoluminescence and Thermally Activated Emission DOI
Asato Mizuno, Ryota Matsuoka, Shojiro Kimura

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(27), P. 18470 - 18483

Published: June 26, 2024

Luminescent radicals have been intensively studied as a new class of materials exhibiting novel photofunctions unique to open-shell systems. When luminescent are assembled, intriguing spin-correlated luminescence phenomena emerge, including excimer-like emission and magnetic-field effects on (i.e., magnetoluminescence, MagLum). However, the underlying mechanisms these arising from spin multiplicity spin-dependent excited-state dynamics poorly understood due limited number polyradical systems available for study. In particular, correlation between stronger intramolecular exchange interactions (|2J/kB| > ∼10 K, where J kB coupling constant Boltzmann constant, respectively) properties has not fully explained. this study, carbazole-containing diradical emitter (1) corresponding monoradical (2) were prepared in-depth study properties, with measurements under magnetic fields up 18 T. Diradical 1 negative 2J/kB value several tens kelvin exhibits single-molecule MagLum thermally activated luminescence, whereas 2 does not. Detailed quantitative analyses revealed that both strongly dominated by ground-state statistics based distribution values). Furthermore, external heavy-atom in heavy-atom-containing solvents such iodobenzene, This is first experimental verification emitters. work demonstrates emitters can be designed degrees freedom ground excited states.

Language: Английский

Citations

8
Mechanochemical driven oxidative desulfurization of high-sulfur petroleum coke over [Bpy]PMoVn coupled with amide-based binary deep eutectic solvents DOI
Yan Wang, Hao Luan,

Jiahong Gong

et al.

Chemical Engineering Science, Journal Year: 2024, Volume and Issue: unknown, P. 121021 - 121021

Published: Nov. 1, 2024

Language: Английский

Citations

6
Spin-State Manipulation in a Luminescent Diradical Polymer DOI
Shengjie Wang, Xing Wang,

Junshuai Ding

et al.

Macromolecules, Journal Year: 2024, Volume and Issue: 57(13), P. 6133 - 6139

Published: June 27, 2024

Controlling the spin states to modulate their optical properties is crucial for spintronics and emerging quantum technologies. Open-shell luminescent diradicals are promising candidates achieving this goal due independent spins. However, spin-optical modulation in traditional still faces significant challenges owing low luminescence efficiency inevitable aggregate effects. In study, we first achieved efficient of a diradical by suspending on polymer main chain. The resulting exhibits high photoluminescence 44.0% condensed state along with excellent photostability. Most importantly, have demonstrated successful spin-state manipulation through temperature control application magnetic field. These findings open up new avenues based materials, providing important guidance development spin-optoelectronics.

Language: Английский

Citations

4
Enhancing the Optically Detected Magnetic Resonance Signal of Organic Molecular Qubits DOI Creative Commons

Yong Rui Poh,

Joel Yuen-Zhou

ACS Central Science, Journal Year: 2025, Volume and Issue: 11(1), P. 116 - 126

Published: Jan. 3, 2025

In quantum information science and sensing, electron spins are often purified into a specific polarization through an optical-spin interface, process known as optically detected magnetic resonance (ODMR). Diamond-NV centers transition metals both excellent platforms for these so-called color centers, while metal-free molecular analogues also gaining popularity their extended lifetimes, milder environmental impacts, reduced costs. our earlier attempt at designing such organic high-spin π-diradicals, we proposed to spin-polarize by shelving triplet MS = ±1 populations singlets. This was recently verified experiments albeit with low ODMR contrasts of <1% temperatures above 5 K. this work, propose improve the signal moving singlet back 0 sublevel, true carbon-based analogue NV center. Our proposal is based upon transition-orbital group-theoretical analyses beyond-nearest-neighbor spin–orbit couplings, which further confirmed ab initio calculations realistic trityl-based radical dimer. Microkinetic point toward high around 30% under experimentally feasible conditions, stark improvement from previous works. Finally, in quest ground-state addressable spin qubits, exemplify how symmetry-based design avoids Zeeman-induced singlet–triplet mixings, setting scene realizing qubit gates.

Language: Английский

Citations

0
Stable Fluorenyl Radicals Showing Tunable Doublet Emission DOI Creative Commons
Xudong Hou, Tingting Xu, Jun Zhu

et al.

Chemistry, Journal Year: 2025, Volume and Issue: 7(1), P. 21 - 21

Published: Feb. 7, 2025

Neutral organic radicals with intrinsic spin-allowed doublet emission have emerged as a promising class of luminescent materials, garnering significant research interest. However, the development stable tunable remains challenging. Herein, we present synthesis series 9-(2,4,6-trichlorophenyl)-substituted fluorenyl functionalized various substituents at 3,6-positions. These exhibit enhanced stability through efficient spin delocalization and kinetic protection. Notably, they display red-shifted photoluminescence compared to traditional polychlorotriphenylmethyl radicals, maximum wavelengths ranging from 679 nm 744 nm. The mechanisms underlying emission, well their electrochemical properties, been thoroughly investigated.

Language: Английский

Citations

0
A Luminescent Stable Triarylmethyl Diradical with an Axially Chiral Spacer DOI Open Access
Yohei Hattori, Ryota Matsuoka,

Atsumi Baba

et al.

Chemistry - A European Journal, Journal Year: 2025, Volume and Issue: unknown

Published: March 6, 2025

Two units of a highly stable luminescent triarylmethyl radical (PyBTM) were bridged using chiral octahydrobinaphthyl moiety, resulting in diradical with sufficient stability to enable the measurement its chiroptical properties. To synthesize this diradical, novel boronic ester precursor, αH-PyBTM-B(Epin), was designed. The use precursor significantly improved yield and streamlined preparation radical-substituted molecules. photoluminescence quantum (PLQY) measured be 10 % chloroform. Furthermore, both circular dichroism (CD) circularly polarized luminescence (CPL) successfully observed.

Language: Английский

Citations

0
Aggregation-Free, Highly Soluble CN-Terminated Dicyclopentadiene-Fused Rylenes DOI

Liuying Jiao,

Ya Zou, Wei Fan

et al.

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

Published: March 7, 2025

Rylenes, known for their excellent photochemical properties, hold great promise in OLEDs, solar cells, and bioimaging applications. However, the solution-phase synthesis of long rylene molecules is often hindered by poor solubility low stability. In this work, we present an efficient synthetic strategy a series CN-terminated rylenes via base-mediated intramolecular Michael addition oxidative cyclodehydrogenation (Scholl reaction). The synthesized feature cyclopentadiene ring at both bay positions each perylene subunit electron-deficient CN groups peri-termini. These structural modifications render stable, aggregation-free, highly soluble. Bulky aryl attached to rings not only improve but also block intermolecular π-aggregation, as revealed XRD analysis. Additionally, electron-withdrawing stabilize π-conjugated system. extended π-conjugation reduces HOMO-LUMO gap, enhancing absorption inducing significant bathochromic shift into NIR I II regions.

Language: Английский

Citations

0
Semiconducting Open‐Shell Radicals for Precise Tumor Activatable Phototheranostics DOI Creative Commons
Jie Zhang,

Haifen Luo,

Wen Ma

et al.

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

Published: March 7, 2025

Semiconducting open-shell radicals (SORs) have promising potential for the development of phototheranostic agents, enabling tumor bioimaging and boosting tumorous reactive oxygen species (ROS). Herein, a new class semiconducting perylene diimide (PDI), designated as PDI(Br)n with various numbers bromine (Br) atoms modified on PDI's bay/ortho positions is reported. demonstrated to transform into radical anion, [PDI(Br)n]•-, in reducing solution, typical g-value 2.0022. Specifically, [PDI(Br)4/6]•- generated weakly reductive tumor-mimicking solution exhibits high stability air. Quantum chemical kinetic simulation ultrafast femtosecond transient absorption spectroscopy indicate that [PDI(Br)6]•- has low π-π stacking energy (0.35 eV), fast electron transfer rate (192.4 ps) gap PDI(Br)6 (ΔES1, T1 = 1.307 eV, ΔES1, T2 0.324 eV) respectively, which together result excited-state charge characters. The nanoparticle radicals, [PDI(Br)6] NPs•-, specifically enable chemodynamic type-I photodynamic ROS generation tumors, including superoxide hydroxyl elicit immunogenic cell death effect. Also, NPs•- facilitate activatable bioimaging-guided therapy due their photoacoustic signal at 808 nm NIR-II emission 1115 nm. work paves way design SORs precise cancer theranostics.

Language: Английский

Citations

0
Diverse Postfunctionalization of Open-Shell Diradicaloids and Impact of Conjugated Functional Substituents on Optoelectronic Properties DOI
Xiao Wang, Lei Tian, Xuejiao Wu

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 23, 2025

Organic radicals are usually incapable of postfunctionalization for structure expansion and optoelectronic property optimizations. Herein, based on a sulfone-embedded skeleton derived from Chichibabin's hydrocarbon, we showcase the regioselective bromination further postmodifications open-shell diradicaloids via diverse palladium-catalyzed nucleophilic substitution, Sonogashira coupling, Stille coupling reactions. Such facile structural expansions yielded series conjugated singlet diradicaloids, showing finely tuned physicochemical characteristics, versatile crystalline-state molecular configurations packing modes, impressive charge-carrier mobility 1.5 cm2/V·s.

Language: Английский

Citations

0
On the Meaning of De‐Excitations in Time‐Dependent Density Functional Theory Computations DOI Creative Commons
Felix Plasser

Journal of Computational Chemistry, Journal Year: 2025, Volume and Issue: 46(8)

Published: March 25, 2025

De-excitations play a prominent role within the mathematical formalism of time-dependent density functional theory (TDDFT) and other excited-state response methods. However, their physical meaning remains largely unexplored poorly understood. It is purpose this work to shed new light on issue. The main thesis developed here that de-excitations are not peculiarity TDDFT but they more fundamental property underlying wave functions reflecting how electrons excited between partially occupied orbitals. paraquinodimethane (pQDM) molecule chosen as convenient model system whose open-shell character can be modulated via twisting its methylene groups. Using one-electron transition matrix rigorous basis for our analysis, we highlight qualitative quantitative parallels in way reflected multireference function computations. As physically observable consequence, lowering dipole moment derives from destructive interference excitation de-excitation contributions. In summary, hope will formal practical aspects regarding application computations, especially diradicaloid systems.

Language: Английский

Citations

0