Acceptor Planarization and Donor Rotation: A Facile Strategy for Realizing Synergistic Cancer Phototherapy via Type I PDT and PTT

ACS Nano, Journal Year: 2022, Volume and Issue: 16(3), P. 4162 - 4174

Published: March 1, 2022

Tumor hypoxia seriously impairs the therapeutic outcomes of type II photodynamic therapy (PDT), which is highly dependent upon tissue oxygen concentration. Herein, a facile strategy acceptor planarization and donor rotation proposed to design I photosensitizers (PSs) photothermal reagents. Acceptor can not only enforce intramolecular charge transfer redshift NIR absorption but also PSs from photochemical pathways. Donor optimizes conversion efficiency (PCE). Accordingly, three 3,6-divinyl-substituted diketopyrrolopyrrole (DPP) derivatives, 2TPAVDPP, TPATPEVDPP, 2TPEVDPP, with different number rotors were prepared. Experimental results showed that compounds excellent PSs, corresponding 2TPEVDPP nanoparticles (NPs) most possessed highest PCE. The photophysical properties NPs are particularly suitable for in vivo fluorescence imaging-guided synergistic PDT/PTT therapy. helpful exploiting phototherapeutic reagents high efficacy PDT PTT.

Language: Английский

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Classification of doubly excited molecular electronic states

Chemical Science, Journal Year: 2023, Volume and Issue: 14(15), P. 4012 - 4026

Published: Jan. 1, 2023

A rigorous classification scheme for doubly excited states is proposed and the different possible types are exemplified in various molecules.

Language: Английский

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Pre‐Endcapping of Hyperbranched Polymers toward Intrinsically Stretchable Semiconductors with Good Ductility and Carrier Mobility

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(19)

Published: Feb. 7, 2024

Abstract The advancement of semiconducting polymers stands as a pivotal milestone in the quest to realize wearable electronics. Nonetheless, endowing semiconductor with stretchability without compromising their carrier mobility remains formidable challenge. This study proposes “pre‐endcapping” strategy for synthesizing hyperbranched (HBSPs), aiming achieve balance between and organic findings unveil that aggregates formed by endcapped network structure not only ensure efficient charge transport but also demonstrate superior tensile resistance. In comparison linear conjugated polymers, HBSPs exhibit substantially larger crack onset strains notably diminished moduli. It is evident surpass counterparts terms both mechanical properties. Among HBSPs, HBSP‐72h‐2.5 out preeminent candidate within field inherently stretchable maintaining 93% its initial even when subjected 100% strain (1.41 ± 0.206 cm 2 V −1 s ). Furthermore, thin film devices remain stable after undergoing repeated stretching releasing cycles. Notably, mobilities are independent directions, showing isotropic behavior. preliminary makes this potential future design materials flexible electronic devices.

Language: Английский

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Parallel triplet formation pathways in a singlet fission material

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: Sept. 6, 2022

Abstract Harvesting long-lived free triplets in high yields by utilizing organic singlet fission materials can be the cornerstone for increasing photovoltaic efficiencies potentially. However, except polyacenes, which are most studied systems field, spin-entangled correlated triplet pairs and born through relatively poorly characterized. By transient absorption photoluminescence spectroscopy supramolecular aggregate thin films consisting of Hamilton-receptor-substituted diketopyrrolopyrrole derivatives, we show that photoexcitation gives rise to formation spin-0 pair 1 (TT) from lower Frenkel exciton state. The existence is proved faint Herzberg-Teller emission enabled vibronic coupling with an artifact-free triplet-state photoinduced near-infrared. Surprisingly, electron paramagnetic resonance reveals produced classical intersystem crossing instead dissociation, two pathways competition. Moreover, comparison triplet-formation dynamics J-like H-like same energetics spin-orbit mediated persists both. only forms film, pinpointing huge impact intermolecular geometry on dynamics.

Language: Английский

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Alternating Donor‐Acceptor Ladder‐Type Heteroarene for Efficient Photothermal Conversion via Boosting Non‐Radiative Decay

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 11, 2024

The development of novel ladder-type conjugated molecules is crucial for advancing supramolecular chemistry and material science. In this study, we report a straightforward synthesis new alternating donor-acceptor (D-A) heteroarene, FCDTDPP, demonstrate its application as photothermal agent imaging cancer therapy. FCDTDPP constructed by vinylene bridge between cyclopentadithiophene (D) diketopyrrolopyrrole (A) through intramolecular Friedel-Crafts type reaction. exhibits unique combination good molecular planarity, efficient intra-/intermolecular mixed D-A interactions, local aromaticity. These features collectively contribute to broad intense absorptions with narrow band gap in red the spectra, coupled multiple vibrational absorption feature, thereby enhancing non-radiative decay process resulting conversion property. nanoparticles (NPs) exhibit superior performance stability under 660 nm laser irradiation. Moreover, vitro studies reveal that NPs possess excellent biocompatibility, low cytotoxicity, robust therapeutic efficacy, finding further corroborated preliminary vivo experiments tumor-bearing mice. This work charts course engineering organic systems, propelling relevant research forward.

Language: Английский

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Carrier Mobility and Luminescence Properties of a One-Step Synthesized π-Extended Diketopyrrolopyrrole Derivative

ACS Omega, Journal Year: 2025, Volume and Issue: unknown

Published: March 11, 2025

This study demonstrates the one-step synthesis of 4,5,11,12-tetrapentyl-7H,14H-thieno[3,2-g]thieno[3′,2':7,8]indolizino[2,1-a]indolizine-7,14-dione (BIPI) from 6-dodecyne and 3,6-di(thiophen-2-yl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione via Ru-catalyzed CH-NH activation, reported by Gońka et al. in 2019. The synthesized BIPI exhibited intense luminescence broad absorption up to 600 nm owing substantial overlap between HOMO LUMO orbitals. high planarity achieved through cyclization further enabled fabrication organic field-effect transistors using vacuum deposition method, demonstrating a hole mobility μh = 1.6 × 10–2 cm2/(V s). Band calculations Quantum ESPRESSO with crystal structure revealed increase valence band dispersion movement holes along columnar direction. ideal carrier is calculated charge transfer rate.

Language: Английский

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Extending the Conjugation of Xanthene Through N Heteroatoms

Dyes and Pigments, Journal Year: 2025, Volume and Issue: unknown, P. 112760 - 112760

Published: March 1, 2025

Language: Английский

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A Fused Diketopyrrolopyrrole Derivative for Single‐Crystal Visible‐NIR Organic Phototransistor

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

Published: March 21, 2025

Organic phototransistors (OPTs) have garnered significant attention due to their potential in wearable and flexible electronics. However, achieving high carrier mobility broadband response organic semiconductors for OPTs remains a challenge. In this work, new fused diketopyrrolopyrrole (FDPP) derivative is reported, 2,9-bis(4-hexylphenyl)-7H,14H-thieno[3',2':7,8]indolizino[2,1-a]thieno[3,2-g]indolizine-7,14-dione (FDPP-p-C6), synthesized through N-cyclization of DPP with an adjacent thiophene unit. This ensures backbone planarity, while the hexyl side chains remain distant from core, minimizing steric hindrance promoting efficient intermolecular stacking. Consequently, single crystals FDPP-p-C6 exhibit planar typical herringbone packing arrangement, facilitating charge transport. The single-crystal field-effect transistors (OFETs) demonstrate p-type transport, maximum 0.20 cm2 V-¹ s-¹. Additionally, show promising performance, responsivity across broad spectral range photoresponsivity 2.2 × 103 A W-¹ along specific detectivity, derived noise current, 2.8 1010 Jones. study highlights FDPP as key material advancing OFET OPT technologies, propelling relevant research forward.

Language: Английский

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Novel Thienyl DPP derivatives Functionalized with Terminal Electron‐Acceptor Groups: Synthesis, Optical Properties and OFET Performance

Chemistry - A European Journal, Journal Year: 2022, Volume and Issue: 28(25)

Published: March 4, 2022

Three novel diketopyrrolopyrrole (DPP) based small molecules have been synthesized and characterized in terms of their chemical-physical, electrochemical electrical properties. All the consist a central DPP electron acceptor core symmetrically functionalized with donor bi-thienyl moieties flanked terminal positions by three different auxiliary electron-acceptor groups. This kind molecular structure, an alternation groups, was purposely designed to provide significant absorption at longer wavelengths visible spectrum: when analysed as thin films, fact, dyes absorb well over 800 nm exhibit narrow optical bandgap down 1.28 eV. A detailed DFT analysis provides useful information on electronic structure features main transitions. Organic field-effect transistors (OFETs) fabricated depositing active layers from solution: end-functionalization had effect charge-transport properties two acting n-type semiconductors (electron mobility up 4.4 ⋅ 10

Language: Английский

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Aryl-Ethenyl-Substituted Diketopyrrolopyrrole Semiconductors with trans Configuration and Ultraclose π-Plane Stacking Distance

Chemistry of Materials, Journal Year: 2024, Volume and Issue: 36(9), P. 4215 - 4225

Published: April 30, 2024

We present a new class of diketopyrrolopyrrole (DPP) derivatives, which comprise the ethenylidene linker that connects DPP unit to aryls, such as thiophene (TE-DPP), furan (FE-DPP), and cyanothiophene (CNTE-DPP), respectively. The introduction linkers led extended π-conjugation length enhanced intramolecular charge transfer, giving rise prominent red shift in visible region spectrum, low-lying lowest unoccupied molecular orbital (LUMO) level, narrow band gap. single-crystal X-ray diffraction analysis reveals resulting compounds exhibit planar configurations with close π–π distances 3.17 Å. Furthermore, these one-dimensional arrangement, benefits from intermolecular hydrogen bonds, facilitating short contact between donor acceptor segments. Organic field-effect transistor (OFET) measurements reveal TE-DPP FE-DPP p-type transport behavior maximum mobility 0.05 0.18 cm2 V–1 s–1, While CNTE-DPP exhibits ambipolar characteristics electron hole mobilities up 0.13 0.24 Our work demonstrates potential aryl-ethenyl-substituted diketopyrrolopyrroles (ArE-DPPs) promising semiconducting materials for applications organic electronic devices.

Language: Английский

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