20 Feb 17:27
by Chen An,
Wanyuan Deng,
Yuan Xie,
Kang An,
Huan Cao,
Dezhi Yang,
Yihui Chen,
Wansheng Liu,
Yuhang Xu,
Ning Li,
Hongbin Wu,
Yong Cao
Incorporating a hole-transporting polymer (TFB) into emissive fluorescent organic emitter Y11 strongly boosts the photoluminescence quantum yields (PLQY) of the film, as well as enhances the light out-coupling efficiency of the device, giving rise to efficient near-infrared OLEDs peaked at 934 nm with external quantum efficiency (EQE) over 1.7%.
Abstract
Near-infrared organic light-emitting diodes (NIR OLEDs) with emission peak above 900 nm are attractive for many emerging applications, spanning from bioimaging to light detection and ranging. However, the device performance of NIR OLEDs is generally limited by the low quantum efficiency of emitters because of the fast nonradiative transition process imposed by energy-gap law and aggregation quenching. So far, only a few Pt(II) complexes delivering external quantum efficiency (EQE) over 1% are reported, while there is no comparable electroluminescence in heavy-metal-free fluorescent organic emitters. Here, NIR OLEDs centered at 934 nm by blending an acceptor–donor–acceptor type molecule Y11 into a polymer host poly[(9,9-dioctylfluorenyl-2,7-diyl)-alt-(4,4′-(N-(4-sec-butylphenyl)diphenylamine) (TFB) are reported. The OLEDs show a remarkably high EQE of 1.72%. Moreover, owing to a low turn-on voltage (≈0.9 V), the resultant NIR OLEDs have an electricity-to-light power efficiency surpassing 20 mW W−1. The improved device performance can be attributed to enhanced photoluminescence quantum yields (PLQYs) of the blends owing to suppressed aggregation quenching, and favorable light extraction from the emissive layer. Such values are the highest among fluorescent OLEDs with electroluminescence above 900 nm.
20 Feb 17:27
by Luoqing Wang,
Han Wang,
Shuai Yu,
Nan An,
Yuyu Pan,
Jing Li,
Tao Jia,
Kai Wang,
Wei Huang
![Manipulating Molecular Motion of [1,2,5]Thiadiazolo[3,4-g]Quinoxaline-6,7-Dicarboxylate Small Molecules for Highly Efficient Solar-Thermal Water Evaporation and Thermoelectric Power Generation](https://onlinelibrary.wiley.com/cms/asset/9b7cbe7d-6750-4382-8746-e43a67d24462/adfm202315762-gra-0001-m.png)
Based on [1,2,5]thiadiazolo[3,4-g]quinoxaline-6,7-dicarboxylate acceptor unit, D–A conjugated organic photothermal materials with wide light spectral absorption range and high photothermal conversion efficiency are developed. The materials can be used for efficient water evaporation, photothermal-electric power conversion, and water-electricity co-generation applications.
Abstract
Organic conjugated molecules are a category of high solar harvesting material that can convert energy into heat and be utilized as solar-driven water-electricity co-generation. However, the limited absorption range and insufficient photothermal conversion efficiency hinder their application. Herein, two new organic molecules TPA-BTQ and TPA-SBTQ, featuring strong electron withdrawing [1,2,5]thiadiazolo[3,4-g]quinoxaline-6,7-dicarboxylate (BTQ) center, terminated by triphenylamine or thiophene-bridged triphenylamine are designed and synthesized. Detailed theory calculations and spectral analysis confirm that the BTQ unit induces strong intramolecular charge transfer and expands the absorption across a wide spectra range. The flexible alky chain substituted on thiophene inhibits the over-aggregation and affords more rotation space, leading to suppressed radiative transition and efficient solar-thermal conversion. Therefore, TPA-SBTQ powder shows broad absorption across 350 to 1300 nm with a high photothermal conversion efficiency of 18.28% under 1 kW m−2 simulated solar irradiation. Moreover, TPA-SBTQ is further explored for solar-thermal conversion applications. The evaporation rate of TPA-SBTQ solar-driven water evaporator can reach a remarkable 1.337 kg m−2 h−1 with 92% of water evaporation efficiency under 1 kW m−2 solar irradiation. This study provides guidance for the rational design of high-efficient organic solar-thermal materials with a wide absorption spectrum and excellent photothermal conversion efficiency at the molecular level for emerging photothermal-related applications.
20 Feb 17:25
by Chen Lu,
Eunkyung Cho,
Keke Wan,
Chunxiao Wu,
Yuhang Gao,
Veaceslav Coropceanu,
Jean‐Luc Brédas,
Feng Li
Here, a series of efficient, stable luminescent radicals is designed and synthesized. The fine-tuning of the chemical structure allows the photoluminescence quantum efficiency (PLQE) to be maximized and nearly reach the theoretical 100% limit in the case of TTM-3,4FCz. This material demonstrates an impressive PLQE of 98.0%, positioning itself among the most outstanding values reported for radicals to date. This achievement stems from the optimization of the effective distance between the donor (D) and acceptor (A) moieties.
Abstract
Donor-acceptor (D–A•) type luminescent organic radicals have received widespread attention as efficient doublet emitters. However, their generally low photoluminescence quantum efficiency (PLQE) and limited photostability restrict their various applications. Since unraveling the relationship between structure and properties of D–A• type luminescent radicals remains a challenge, here, a series of tri(2,4,6-trichlorophenyl)methyl (TTM) radical derivatives, which differ by the location of their ring fusion sites and nature of their heteroatoms, is synthesized. The PLQE of isomers varies by ten times as a function of ring fusion sites. In particular, the PLQE of a radical undergoing ring fusion at the carbazole 3,4-position is as high as 98.0%. Quantum-chemical calculations show that in the case of overlapping holes and electrons, by increasing the effective distance between the D and A moieties, the radiative transition rates of the radicals increase. Also, decreasing the electronic coupling between the charge-transfer and local-excited states and avoiding large geometrical distortions between the ground state (D0)_and the first excited state (D1) can significantly reduce the nonradiative transition rates. This work offers a design strategy to obtain efficient and stable luminescent radicals by modifying the sites of ring fusion, which allows control of the radiative and nonradiative transition rates.
20 Feb 17:24
by Zhilong He,
Yi Zhang,
Yi Lin,
Siyuan Li,
Shimin Zhang,
Zhongyuan Xue,
Zhe Hao,
Zheng Tang,
Hongliang Zhong
Differing from the previous fluorinated photovoltaic materials that C(sp2)─F bonds in conjugated backbone or C(sp3)─F bonds in sidechains, this work develops a new molecular design concept by introducing polyfluoride units containing C(sp3)─F bonds into the backbone, which would not affect the conjugation but enhance the intermolecular interaction. Thus, the relevant fluoropolymers exhibit superior performance in the ternary organic solar cells.
Abstract
Fluorination strategy is demonstrated to be a successful approach for optimizing the electron distribution and morphology of organic photovoltaic materials. The previous works focus on introducing only a few C(sp2)─F bonds into conjugated backbone or C(sp3)─F bonds into sidechains. Herein, a new strategy by introducing C(sp3)─F polyfluoride unit into the backbone is proposed, wherein the fluorine atoms are not involved into the conjugation but can promote the intermolecular interaction between backbones. Two wide-bandgap fluoropolymers are prepared and employed as the third component for ternary organic solar cells. As expected, even if there are six fluorine atoms in a single repeat unit, the relevant fluoropolymers possess complementary absorption and aligned energy levels. More importantly, the polyfluoride backbone affords adequate non-covalent interactions, consequently enhancing the polymer aggregation and packing order, which is verified by a fibril-like morphology in the blend film with the host polymer PM6 and only 10 wt.% fluoropolymer. In addition, the decreased surface energy caused by polyfluoride unit is beneficial for the improvement of domain purity and the formation of nanoscale phase separation between donor and acceptor materials. As a result, the fluoropolymer-assisted ternary device displays a higher efficiency of 18.74% compared with the binary device (17.39%).
20 Feb 17:23
by Nayara Méndez‐Gil,
Sergio Gámez‐Valenzuela,
Marcelo Echeverri,
Gary H. Suyo,
Marta Iglesias,
M. Carmen Ruiz Delgado,
Berta Gómez‐Lor
Four novel donor-acceptor truxene-based porous polymers including a benzothiadiazole group as electron-deficient unit have been synthesized, exhibiting potential applications in defense-related areas. Specifically, one of the polymers displays a remarkable ability to detect explosive nitraoaromatics while another shows efficient photocatalytic activity in the aerobic sulfoxidation of the sulfur mustard simulant 2-chloro-ethyl sulfide (MGS).
Abstract
Four donor-acceptor (D-A) polymers are synthesized by combining two different electron donors (truxene and its more electron rich triaza analogue, triindole) with an electron-deficient monomer (benzothiadiazole) through two different positions (2,7,13 or 3,8,13) and their optoelectronic properties are studied by theoretical and experimental methods. One of the polymers exhibits remarkable sensing capabilities for explosive nitraoaromatics while another demonstrated efficient photocatalytic activity in the aerobic sulfoxidation of the sulfur mustard simulant 2-chloro-ethyl ethyl sulfide (MGS) sulfoxidation. These results highlight their potential applications in defense-related areas. Moreover, the structure-performance relationships observed among the four polymers have enabled us to deepen the understanding of the mechanisms underlying the performance of these polymers in the aforementioned applications, thereby providing valuable insights to further improve their properties.
20 Feb 17:19
Chem. Sci., 2024, 15,2755-2762
DOI: 10.1039/D3SC05941C, Edge Article
Open Access
Alba Sanz-Velasco, Olivia Amargós-Reyes, Aya Kähäri, Sophia Lipinski, Luca M. Cavinato, Rubén D. Costa, Mauri A. Kostiainen, Eduardo Anaya-Plaza
In this work, we study the interplay between hydrophilicity/hydrophobicity in cationic aggregation induced emitters, and their application in light emitting electrochemical cells.
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20 Feb 17:17
Chem. Sci., 2024, 15,4054-4067
DOI: 10.1039/D3SC06552A, Edge Article
Open Access
Fatima Hameed, Arindam Maity, Victor S. Francis, Nagarjuna Gavvalapalli
Overcoming synthetic challenges, we present the synthesis of previously undiscovered and highly coveted conjugated pyrazinacene polymers. The LUMO energy levels in these polymers rival those of some of the best-known n-type polymers.
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20 Feb 13:45
Chem. Sci., 2024, 15,4364-4373
DOI: 10.1039/D3SC05533G, Edge Article
Open Access
Qiuyan Liao, Aisen Li, Arui Huang, Jiaqiang Wang, Kai Chang, Hehua Li, Pengfei Yao, Cheng Zhong, Peidong Xie, Jinfeng Wang, Zhen Li, Qianqian Li
In situ regulation of π–π coupling was realized with the combination of rigid intramolecular dimer models and external stimuli, mainly due to the balance of π–π and solvent–π interactions. The results establish the quantitative relationship between emission properties and π–π distances.
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20 Feb 13:44
Chem. Sci., 2024, 15,4171-4178
DOI: 10.1039/D3SC06271F, Edge Article
Open Access
Jiaying Cui, Syed Husnain Ali, Zhuoyao Shen, Wensheng Xu, Jiayi Liu, Pengxiang Li, Yang Li, Ligong Chen, Bowei Wang
A series of ε-polylysine-based room-temperature phosphorescent materials were constructed by simple doping, which realized the characteristics of ultra-long life, adjustable colour, and excitation- and time-dependent afterglows.
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23 Jan 13:19
by Zhong Zheng,
Lu Wang,
Yangyang Xin,
Qi Wang,
Xiangchen Hong,
Yuewei Zhang,
Shek‐Man Yiu,
Fan Zhou,
Jie Yan,
Dongdong Zhang,
Lian Duan,
Yun Chi
Blue Ir(III) phosphors f-ct7a–c bearing purinylidene chelates are synthesized, among which the organic light-emitting diode (OLED) based on f-ct7c exhibits external quantum efficiency (EQEmax) 26.6% and EQE of 22.3% at 1000 cd m‒2, while hyper-OLED based on f-ct7b and t-DABNA achieves EQEmax of 36.1% and CIE(
x
,
y
) of 0.14, 0.09.
Abstract
It is envisioned that the efficient and stable blue OLED phosphors can be synthesized using Ir(III) complexes with electron-deficient carbene cyclometalates. Therefore, three facially coordinated Ir(III) phosphors f-ct7a- c bearing isomeric purinylidene chelates are obtained. They possess three, two, and one 4-t-butylphenyl cyclometalate together with the same number of N-phenyl appendage on carbene fragments, and exhibit photoluminescence centered (λ
max) at 452‒461 nm, fast radiative rate constants (k
r) of 7.5–11.3 × 105 s‒1, and high quantum yield (PLQY) up to 80% in degassed toluene at RT. Representative OLED based on f-ct7c gives maximum external quantum efficiency (EQEmax) of 26.6%, CIE(
x
,
y
) of 0.16, 0.15, and low roll-off with EQE of 22.3% at 1000 cd m‒2. Furthermore, they can be utilized to sensitize a deep blue multiple resonance thermally activated delay fluorescence emitter (MR-TADF), i.e., t-DABNA. The corresponding hyper-OLED device based on alternative f-ct7b realizes an EQEmax of 36.1%, CIE(
x
,
y
) of 0.14, 0.09, and full width at half maximum (FWHM) of 26.5 nm. To the understanding, this is the first report on concurrent achieving both the high EQE and small CIE
y
value for Ir(III)-based phosphors.
23 Jan 13:18
by Zhen Hu,
Lili Feng,
Piaoping Yang
The molecular design strategies are systematically review of BTD derivative small molecule NIR-II fluorophores, including the fluorophores with BBTD/BSBT as acceptor and the recently reported novel TQ derivative fluorophores. In addition, the recent applications of BTD derivative NIR-II fluorophores including cancer imaging, PDT/PPT therapy, imaging-guided surgery, disease diagnosis, and angiography are also presented.
Abstract
Second near-infrared (NIR-II) bioimaging technology shows broad application prospects in the field of biomedical due to its significant superiority in deep tissue penetration and high signal-to-background ratio. Among them, organic small molecule fluorophores have received progressively more consideration due to their low biotoxicity, high biocompatibility, rapid clearance, and good modification properties. As the key acceptor core, 2, 1, 3-benzothiadiazole (BTD) derivative plays an essential role in the construction of donor-acceptor-donor type NIR-II fluorophores. This mini-review summarizes the research development of NIR-II small molecule fluorophores based on BTD derivatives in the field of bioimaging, focusing on molecular design and photophysical properties, and introduces a part of the applications in the biological field. Furthermore, the challenges of BTD-based NIR-II fluorophores in the future development and application are discussed
.
23 Jan 13:17
by Dengli Chen,
Cheng Bao,
Liangliang Zhang,
Qiaona Zhang,
Zhiyin Wu,
Zheng‐Yi Li,
Xiao‐Qiang Sun,
Leyong Wang,
Tangxin Xiao
A spirocyclic-scaffold-bridged cyanostilbene dimer (SDCS) is designed and synthesized, which exhibits multiple fluorescence properties: excited-state intramolecular proton-transfer (ESIPT), aggregation-induced emission enhancement (AIEE), and time-dependent self-assembly induced emission (TD/SAIE). Based on the ESIPT-AIEE-TD/SAIE triple fluorescence mechanism, SDCS can be used for time-dependent information encryption and two-color fluorescence imaging of latent fingerprints.
Abstract
Organic luminescent materials with time-dependent emission colors show promising applications in the fields of chemical sensing, high-resolution bioimaging, and high-security information encryption. Herein a time-dependent fluorescence system based on a spirocyclic scaffold-bridged cyanostilbene dimer (SDCS) as the single component in a mixed CH3CN/H2O solvent is presented. Specifically, the original orange-emitting nanoparticles prepared from SDCS by reprecipitation can transform into green-emitting nanosheets over time driven by supramolecular self-assembly. It is worth noting that such a transformation rate can be controlled by tuning the water fraction. Based on these unique properties, fluorescent binary codes are developed, enabling time-dependent information encryption with a higher level of security. Moreover, the dual color can be individually fixed by solid matrices such as hydrogel or powder. The obtained luminescent powders are successfully used in two-color fluorescence imaging of latent fingerprints. This work demonstrates the use of a supramolecular strategy to control multiple emissions in a single-component system for multifunctional applications.
23 Jan 13:16
by Seongyeon Yang,
Gyumin Jang,
Chan Uk Lee,
Jaehyun Son,
Junwoo Lee,
Wooyong Jeong,
Dong Gue Roe,
Jeong Ho Cho,
Jooho Moon
An antisolvent dripping strategy is employed to fabricate chiral 1D (S-MBA)PbI3 (MBA = methylbenzylamine) perovskites. The crystallization process of a perovskite and the density of its structural defects can be controlled by the choice of antisolvent. By using chloroform as the antisolvent, iodine vacancies are effectively suppressed and the inorganic framework is distorted, producing a highly circularly polarized light-active chiral perovskite.
Abstract
Chiral perovskites have emerged as promising next-generation materials for polarization detection due to their excellent circularly polarized light (CPL) detection capabilities. However, they suffer from a low chiroptical response when fabricated as a polycrystalline thin film, limiting their potential range of applications. Herein, it is demonstrated that antisolvent dripping during the spin-coating process can effectively improve the chiroptical properties of polycrystalline chiral perovskite thin films. Systematic analysis with different antisolvents reveals that the highly polar antisolvent chloroform interacts with dimethyl sulfoxide molecules via hydrogen bonding. This strong hydrogen bonding suppresses the formation of intermediate and secondary phases and accelerates the crystallization of chiral 1D perovskites, thus reducing the density of the iodine vacancies inside the perovskite thin films. The lower density of iodine vacancies also intensifies the asymmetric tilting inorganic distortion of PbI6 octahedrons, enhancing the chiroptical response of the fabricated chiral perovskite material. Photodetectors based on the chloroform-treated chiral perovskite films achieve a remarkably high distinguishability of 0.31, outperforming previously reported photodetectors based on the chiral perovskites. The fabricated photodetectors also exhibit outstanding responsivity and detectivity with enhanced operational stability.
23 Jan 13:12
by Xueying Lu,
Qingyang Wang,
Xinliang Cai,
Yupei Qu,
Zhiqiang Li,
Chenglong Li,
Yue Wang
Two pairs of exciplexes are developed as hosts for constructing green organic light-emitting diodes (OLEDs) with high efficiency and color purity. The OLEDs achieve ultrapure green emission with a peak wavelength of 532 nm, full-width at half-maximum of 36 nm, high external quantum efficiency (EQE) of 35.7%, and reduced efficiency roll-off with EQE of 31.0% at 1000 cd m−2.
Abstract
A carbazole-based hole-transport-type (p-type) host, BPhCz, is developed using a nonsymmetrical connection strategy between two identical groups. Two benzimidazole–triazine-based electron acceptor materials with superior electron transport abilities, namely SFX-PIM-TRZ and DSFX-PIM-TRZ, are designed to fabricate exciplex-host systems combined with BPhCz. Exciplexes exhibit excellent carrier transport characteristics and appropriate energy levels and can serve as hosts for green multiple resonance-induced thermally activated delayed fluorescence (MR-TADF) devices. Efficient green MR-TADF organic light-emitting diodes with high color purity and low efficiency roll-offs are successfully fabricated using the exciplexes prepared from BPhCz:SFX-PIM-TRZ and BPhCz:DSFX-PIM-TRZ as hosts, which show low driving voltages of 2.6 and 2.7 V, high maximum external quantum efficiencies (EQEs) of 35.7% and 35.5%, ultrapure green emission with Commission Internationale de L'Eclairage coordinates of (0.27, 0.69) and (0.28, 0.69), and high EQEs of 31% and 30.5% at 1000 cd m−2, respectively.
23 Jan 13:11
by Xiaolong Zeng,
Zongwei Zhang,
Yun‐Shuai Huang,
Jiangli Fan,
Xiaojun Peng,
Si Wu,
Wen Sun
Two Ru metalloprodrugs, Ru-3XOEG and Ru-PEG, respectively are designed for enhanced phototherapy. Ru-3XOEG with dendritic ethylene glycol (EG) self-assembles into large compound micelles, while Ru-PEG with linear EG self-assembles into vesicles. The self-delivered Ru-3XOEG and Ru-PEG circulate in the bloodstream and accumulate at tumor sites. Red-light irradiation induces Ru-H2O release and 1O2 generation, inhibiting tumor growth.
Abstract
Small-molecule ruthenium (Ru) complexes exhibit limitations in terms of nonspecific delivery, rapid metabolism, and low tumor accumulation. Their delivery can be improved through physical encapsulation into nanocarriers via hydrophobic forces, metallophilic interactions, or π–π stacking interactions. However, delivering Ru complexes for efficient therapy is substantially hindered by potential leakage of drugs, low drug-loading capacity, or batch-to-batch variations. Moreover, current metalloprodrug-based self-delivery systems necessitate supramolecular interactions, which are unsuitable for Ru complexes because of their octahedral structures. Herein, two self-assembled molecular Ru drugs, Ru-3XOEG and Ru-PEG, are reported. Ru-3XOEG involves a three-arm dendritic oligo(ethylene glycol) (OEG), while Ru-PEG involves a linear poly(ethylene glycol) (PEG) chain. Furthermore, these drugs contain an anticancer Ru moiety and a planar pyrene moiety to render hydrophobic forces and π–π stacking supramolecular interactions. Ru-3XOEG self-assembles into large compound micelles. Ru-PEG self-assembles into vesicles. These Ru-containing self-delivered systems exhibit well-defined structures, high Ru loading contents, and long circulation in blood without external nanocarriers. Red light irradiation induces the release of Ru-H2O anticancer agents and the generation of 1O2 to inhibit tumor growth. The presented design of self-assembled molecular Ru complexes opens avenues for the concept of self-delivered metalloprodrugs.
23 Jan 13:10
Chem. Sci., 2024, 15,466-476
DOI: 10.1039/D3SC02685J, Edge Article
Open Access
Yannik Appiarius, Sandra Míguez-Lago, Pim Puylaert, Noah Wolf, Sourabh Kumar, Martin Molkenthin, Delia Miguel, Tim Neudecker, Michal Juríček, Araceli G. Campaña, Anne Staubitz
The presented penta- and hexahelicenes with two boron–nitrogen groups resemble their all-carbon analogs structurally but show considerably improved (chir)optical properties like absorptivities, quantum yields and luminescence dissymmetries.
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23 Jan 13:10
Chem. Sci., 2024, 15,490-499
DOI: 10.1039/D3SC05514K, Edge Article
Open Access
Renny Mathew, Aniruddha Mazumder, Praveen Kumar, Julie Matula, Sharmarke Mohamed, Petr Brazda, Mahesh Hariharan, Brijith Thomas
An interdisciplinary approach to derive the structure of a disordered supramolecular system.
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23 Jan 13:09
Chem. Sci., 2024, 15,2984-2989
DOI: 10.1039/D3SC05171D, Edge Article
Open Access
Matthias Schnitzlein, Kazutaka Shoyama, Frank Würthner
Synthesis and characterization of the first configurationally stable pristine boron-doped helicene, a bora[6]helicene, is described.
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23 Jan 13:05
Chem. Sci., 2024, 15,2778-2785
DOI: 10.1039/D3SC05485C, Edge Article
Open Access
Wenlin Jiang, Ming Liu, Yanxun Li, Francis R. Lin, Alex K.-Y. Jen
Lewis-basic oxygen and sulfur heteroatoms are introduced to novel asymmetric self-assembled monolayers, realizing enhanced packing, effectively adjusting ITO work function, and passivating buried interface in inverted perovskite solar cells.
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23 Jan 13:04
Chem. Sci., 2024, 15,2946-2953
DOI: 10.1039/D3SC06242B, Edge Article
Open Access
Run-Tan Gao, Shi-Yi Li, Bing-Hao Liu, Zheng Chen, Na Liu, Li Zhou, Zong-Quan Wu
Well-defined block copolymers containing helical poly(acyl methane) and π-conjugated poly(phenylene ethynylene)s were facilely prepared, which self-assembly into chiral supramolecular architectures with circularly polarized luminescence.
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02 Jan 18:00
by Quanyou Feng,
Shoujia Zhu,
Bingyang Wang,
Fan Yu,
Hao Li,
Mengna Yu,
Man Xu,
Linghai Xie
TADF macrocycles are classified into four distinct categories: TICT-TADF, TSCT-TADF, MR-TADF macrocycles, and macrocycles for TADF exciplexes. This comprehensive review aims to provide valuable insights into the world of macrocyclic TADF systems, offering a clear understanding and inspiration for researchers in the field of optoelectronic materials.
Abstract
Macrocyclic compounds have garnered considerable attention in the realms of supramolecular chemistry and optoelectronic materials owing to their distinctive geometries, exceptional stability, and potential chiral properties. As third-generation organic light-emitting diodes (OLEDs) emitters, thermally activated delayed fluorescence (TADF) materials present themselves as promising contenders due to their ability to achieve complete exciton utilization through the harnessing of triplet excitons. The incorporation of macrocyclic structures with TADF characteristics holds the potential to yield TADF emitters endowed with unique attributes, thereby synergistically enhancing the performance and longevity of TADF materials for diverse device applications, ultimately propelling their commercialization. Within this comprehensive review, a thorough exploration of the molecular structures, synthesis methodologies, structure-property relationships, and applications of the reported macrocyclic TADF systems in OLEDs are delved. Additionally, the prevailing challenges and prospective research directions are highlighted that demand attention in the realm of macrocyclic TADF materials. It is hoped that this review will provide researchers engaged in optoelectronic materials research with a lucid comprehension and inspiration concerning the intricacies of these macrocyclic TADF systems.
02 Jan 17:59
by Yongmin Jeon,
Tae‐Yun Lee,
Minwoo Nam,
Hyeongjun Lee,
Hyeunwoo Kim,
Sun‐Woo Lee,
Seung Jin Oh,
Seungyeop Choi,
Jun‐Yeong Yang,
Sunghoon Jung,
Seunghun Lee,
Eun‐Yeon Byeon,
Taek‐Soo Kim,
Heonsu Jeon,
Jeong Hyun Kwon
The ion-beam-treated functional polymersubstrate has an optical haze of >70% and is also superhydrophobic. Furthermore, a multifunctional multibarrier that canovercome the disadvantages of polymer substrate is developed. The encapsulation, based on an atomic-layer-deposited nanolaminateand functional polymer, achieves a water vapor transmission rate of 10–6 g m–2 day–1 and UV transmittance of 3%, providing a mechanically andenvironmentally robust multibarrier.
Abstract
As transparent, flexible, and wearable organic electronics degrade under normal outdoor environmental conditions (e.g., water vapor, oxygen, and UV light) and extreme environments, including washing or rain, a customized encapsulation technology is required to improve device reliability. Herein, a simple process is presented for fabricating multifunctional hazy substrates (MFHSs) with excellent gas diffusion barrier (GDB), flexibility, UV reflectance, light scattering, and waterproof properties. First, a spiky polyethylene terephthalate (PET) surface is produced with 76.0% optical haze through ion-beam treatment followed by the formation of a hydrophobic layer to achieve a waterproof effect (contact angle: 153.3°). Then, a multifunctional multibarrier film is fabricated based on a nano-laminated distributed Bragg reflector and functional polymer on the functional PET substrate to serve as a GDB and UV filter. This multibarrier film has excellent mechanical and chemical stabilities, in addition to having a water vapor transmission rate of 10−6 g m−2 day−1 and UV transmittance of <3%. The so-fabricated MFHS not only increases the device efficiency by 73% but also enables a highly flexible and environmentally stable organic light–emitting diode. The surface treatment and encapsulation technologies developed in this study are expected to increase the lifetime of organic devices and facilitate high outdoor usability.
02 Jan 17:59
by Xun Lin,
Zhihong Sun,
Shiyun Huang,
Chuyao Liu,
Jin Peng,
Yueying Li,
Yue Xiong,
Hong Gao,
Jianwei Chen,
Junyang Qi,
Chengming Sun,
Lintao Cai,
Guanjun Deng,
Wenbin Deng
Engineered microglia-exosomes AIE nanoparticles (EE@Fs-NPs) are formed by encapsulating highly twisted AIE photothermal agents with microglia-exosomes (MG-Exo) overexpressing immune checkpoint LAG3 inhibitory antibody (anti-LAG3). EE@Fs-NPs successfully delivered anti-LAG3 to glioblastoma. Anti-LAG3 reversed T cell exhaustion and inhibited heat shock proteins expression, enhancing the efficiency of mild photothermal therapy (PTT). Mild PTT also increased the responsiveness to immune checkpoint blockade therapy.
Abstract
Immune checkpoint blockade (ICB) therapy has achieved remarkable therapeutic effects in cancer, but it is not effective in glioblastoma (GBM). The main reason is that it is difficult for drugs to penetrate blood-brain-barrier (BBB) to GBM and lacks enough pre-existing cytotoxic CD8+ T cells in GBM microenvironment. Here, two AIE photothermal agents (Fs and Fo) are synthesized with NIR-II fluorescence emission and increase molecular twisting of AIE photothermal agents by simply changing one O atom into S atom, improving Fs photothermal conversion efficiency to 48%. Subsequently, engineered microglia-exosomes AIE nanoparticles (EE@Fs-NPs) are prepared by encapsulating Fs with microglia-exosomes which express immune checkpoint LAG3 inhibitory antibody (anti-LAG3) via genetic engineering technology. Engineered microglia-exosomes endow that EE@Fs-NPs cross BBB and target GBM, which successfully deliver anti-LAG3 to GBM. Anti-LAG3 highly reverses T cells exhaustion and generates TNF-α for inhibiting the expression of heat shock proteins to enhance tumor cells thermosensitivity. Moreover, AIE photothermal agents of EE@Fs-NPs generate mild photothermal therapy to destroy tumor cells and improve the infiltration of cytotoxic CD8+ T cells in GBM, which increases the responsiveness of ICB therapy. EE@Fs-NPs produce powerful mild photothermal-immune synergistic therapeutic effect, which will provide a therapeutic platform for the efficient treatment of GBM.
02 Jan 17:58
by Bing‐Huang Jiang,
Zhen‐Jie Gao,
Chien‐Yu Lung,
Zhong‐En Shi,
He‐Yun Du,
Yu‐Wei Su,
Hui‐Shan Shih,
Kun‐Mu Lee,
Hsin‐Huai Hung,
Choon Kit Chan,
Chih‐Ping Chen,
Ken‐Tsung Wong
Remarkable results are attained in indoor Perovskite Solar Cells, achieving an impressive efficiency of 39.9% (3000K LED (1000 lux)) through the application of an A–D–A-type molecule for defect passivation within the electron transport layer.
Abstract
The passivation of perovskite interfacial defects by the electron transport layer (ETL) has emerged as an effective strategy for enhancing the performance of perovskite solar cells (PSCs). Dithieno[2,3-d:2′,3′-d′]thieno[3,2-b:3′,2′-b′]dipyrrole (DTPT)-based acceptor-donor-acceptor (A–D–A) molecules composed of coplanar heteroacene as electron-donating core end-capped with various electron-accepting moieties are designed and examined as ETL modifiers for PSCs. Employing PCBM:DTPTCY as the ETL results in passivation perovskite defects, facilitation energy alignment at the ETL/perovskite interface, and enhancement of carrier transport efficiency. The optimized blended ETL-based Cs0.18FA0.82Pb(I0.8Br0.2)3 p-i-n PSC exhibit performances of 37.2% and 39.9% under TL84 and 3000K LED (1000 lux), respectively. The DTPTCY-based device demonstrates remarkable stability, retaining 87% of its initial power conversion efficiency (PCE) after 30 days of storage in a 40% relative humidity (RH) ambient air environment without any encapsulation, surpassing the control device, which retains only 67% of its original PCE. These findings underscore the potential of A–D–A-type molecule-based interface modification to enhance passivation and contact properties, ultimately leading to high-efficiency and stable PSCs.
26 Dec 15:45
by Zece Zhu,
Zihan Luo,
Yu‐Qing Xie,
Yiting Sun,
Li Xu,
Qi Wu
Host-guest thermally activated delayed fluorescence nanoparticles are assembled with cell-penetrating peptides for fast biological imaging. With highly efficient long-lived fluorescence, real-time in vivo time-resolved luminescence imaging of zebrafish activity is achieved on a chopper-based wide-field microscope, avoiding the strong autofluorescence from organisms.
Abstract
Thermally activated delayed fluorescence (TADF) nanoparticles are used importantly in time-resolved luminescence imaging for eliminating the background signals from scattering and short-lived autofluorescence. However, TADF nanoparticles are seldom used for real-time time-resolved luminescence imaging, due to their limited luminescence efficiency and lifetimes. To detect delayed fluorescence, multiple excitation cycles with adequate delay times are usually required, leading to long detecting durations and low imaging speed. Herein, highly efficient red TADF nanoparticles are developed through doping a guest molecule, TPAAQ (2,6-bis[4-(diphenylamino) phenyl] anthraquinone), in a host (4,4′-bis(carbazol-9-yl)biphenyl, CBP) matrix. With a low doping concentration, the nanoparticles can exhibit obvious TADF with luminescence lifetimes over 0.1 ms and photoluminescence quantum yield up to 35%. A cell-penetrating peptide is used together with the amphiphilic compound for assembling nanoparticles, which can easily penetrate cells and greatly increase the TADF signals for luminescence lifetime imaging. Thanks to the long-lived and highly efficient TADF, real-time in vivo time-gated luminescence imaging of zebrafish is realized on a chopper-based wide-field microscope. This low-cost time-resolved luminescence imaging method showed a great potential for real-time detection of life activities in many organisms with high autofluorescence.
26 Dec 15:43
Chem. Sci., 2024, 15,906-913
DOI: 10.1039/D3SC05034C, Edge Article
Open Access
Aida Yahagh, Ram R. Kaswan, Shahrzad Kazemi, Paul A. Karr, Francis D'Souza
Symmetry breaking charge transfer followed by charge separation with appreciable lifetimes has been demonstrated in a newly synthesized bisstyrylBODIPY dimer in polar solvents using pump-probe and other techniques.
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26 Dec 15:42
Chem. Sci., 2024, 15,102-112
DOI: 10.1039/D3SC02450D, Edge Article
Open Access
Subhadeep Das, Abhilasha Batra, Subhankar Kundu, Rati Sharma, Abhijit Patra
A TADF-emitter was employed to unveil the lysosomal polarity variations during interorganelle interactions and was demonstrated as an indicator to probe complex biological processes like aging through intracellular lifetime imaging.
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12 Dec 17:00
Chem. Sci., 2024, 15,545-554
DOI: 10.1039/D3SC05188A, Edge Article
Open Access
Pagidi Sudhakar, Abhishek Kumar Gupta, David B. Cordes, Eli Zysman-Colman
We report rare examples of organic small molecules exhibiting both thermally activated delayed fluorescence (TADF) and wide-ranging piezochromism (Δλ > 150 nm) in the near-infrared region and their utilization in deep-red OLEDs.
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12 Dec 16:59
Chem. Sci., 2024, 15,940-952
DOI: 10.1039/D3SC05041F, Edge Article
Open Access
Han Sun, Lukun Li, Ruihua Guo, Zhe Wang, Yanhui Guo, Zhiliang Li, Fengling Song
This work demonstrates a novel strategy to address the notorious ACQ of non-AIE type fluorophores in an aqueous medium through deep insights into the structural effects leading to anti-ACQ properties, which could benefit the potential applications.
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12 Dec 16:59
Chem. Sci., 2024, 15,1283-1296
DOI: 10.1039/D3SC04795D, Edge Article
Open Access
Alexander T. Gilligan, Raythe Owens, Ethan G. Miller, Nicholas F. Pompetti, Niels H. Damrauer
We report upconversion for a rigid tetracene dimer that yields 20× that of a monomer model. This is due to a 30× relative enhancement in TTA, indicating participation by intramolecular multiexciton states, including the 5TT, in productive channels.
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