A near-infrared luminescent organic radical with switchable emission and SOMO-HOMO inversion via protonation/deprotonation process

IF 2.9 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics Pub Date : 2025-04-23 DOI:10.1039/d5cp00399g

Obolda Ablikim, Parida Hazretomar, Mehrigul Abdulahat, Fudong Ma, Ayixiemuguli Tuersun, Zhaoze Ding, Zhuoyang Hu

引用次数: 0

Abstract

We synthesized a novel NIR-emissive (785 nm) D-A•-type triphenylmethyl radical TTM-EMICz using a rigidly structured and large-conjugated donor 6-butylindolo[3,2-b]carbazole (ICz) unit. Studies showed that the non-Aufbau electronic structure and PL spectra of the radical can be regulated by the protonation process, in which the PL spectra of the radical can be adjusted to the visible region. Furthermore, the protonated radical TTM-EMICz shows emission centered at 610 nm and 633 nm with PLQY of 4.5 % and 14.9 % in cyclohexane and toluene, with excited state CT properties. The photostability investigation indicated that radical TTM-EMICz has 350 times higher photostability in cyclohexane compared to the well-known carbazole-capped radical TTM-1Cz. This is the first reported near-infrared organic radical with two-state-emissive characteristics (non-Aufbau and Aufbau electronic states), which can be adjusted by protonation/deprotonation process.

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一种近红外发光有机自由基，通过质子化/去质子化过程具有可切换发射和SOMO-HOMO反转

采用刚性结构的大共轭给体6-丁基林多洛[3,2-b]咔唑（ICz）单元合成了一种新型近红外发射（785 nm） D-A•型三苯基甲基自由基TTM-EMICz。研究表明，质子化过程可以调节自由基的非aufbau电子结构和PL谱，其中自由基的PL谱可以调整到可见区。此外，质子化自由基TTM-EMICz在610 nm和633 nm发射中心，环己烷和甲苯的PLQY分别为4.5%和14.9%，具有激发态CT性质。光稳定性研究表明，自由基TTM-EMICz在环己烷中的光稳定性比咔唑基自由基TTM-1Cz高350倍。这是首次报道的具有两态发射特性的近红外有机自由基（非Aufbau和Aufbau电子态），可以通过质子化/去质子化过程进行调节。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Physical Chemistry Chemical Physics 化学-物理：原子、分子和化学物理

CiteScore

5.50

自引率

9.10%

发文量

2675

审稿时长

2.0 months

期刊介绍： Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.