Robust free-base and metalated corrole radicals with reduction-induced emission

IF 9.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chinese Chemical Letters Pub Date : 2024-07-23 DOI:10.1016/j.cclet.2024.110292

Pengfei Li , Chulin Qu , Fan Wu , Hu Gao , Chengyan Zhao , Yue Zhao , Zhen Shen

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引用次数: 0

Abstract

Preparing free-base porphyrinoid radicals that can function as coordination ligands is a challenging task. Here we report the synthesis of a stable, free-base benzocorrole (BC) radical containing only two inner NH protons via a retro-Diels-Alder conversion. The radical character of BC was fully supported by crystallographic analysis, spectroscopic evidence, and theoretical calculations. This neutral radical ligand allowed easy insertion of Zn(II), Ga(III), and Pd(II) ions to produce radical complexes. All these radicals exhibited luminescence-on responses under weak reducing atmosphere, corresponding to the conversion to their aromatic anions. The red fluorescence was observed for BC and its Zn(II) and Ga(III) complexes, and the near-infrared phosphorescence (>900 nm) was detected for Pd(II) complex at room temperature. Furthermore, Ga(III) corrole exhibited a variation in fluorescence in response to axial coordination. Our findings provide a promising radical platform for coordination and developing novel functional materials with switchable spin and emission.

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具有还原诱导发射功能的强效游离基和金属化珊瑚自由基

制备可用作配位体的自由基卟啉基是一项具有挑战性的任务。在此，我们报告了通过逆-Diels-Alder 转化法合成稳定的、仅含两个内部 NH 质子的自由基苯并吡咯（BC）自由基的情况。晶体学分析、光谱证据和理论计算充分证明了 BC 的自由基性质。这种中性自由基配体很容易插入 Zn(II)、Ga(III) 和 Pd(II) 离子，生成自由基配合物。在弱还原气氛下，所有这些自由基都表现出发光反应，相当于转化为它们的芳香阴离子。在室温下，BC 及其 Zn(II) 和 Ga(III) 复合物可发出红色荧光，Pd(II) 复合物可发出近红外磷光（900 nm）。此外，Ga(III)络合物的荧光随轴向配位的变化而变化。我们的研究结果为配位和开发具有可切换自旋和发射的新型功能材料提供了一个前景广阔的自由基平台。

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来源期刊

Chinese Chemical Letters 化学-化学综合

CiteScore

14.10

自引率

15.40%

发文量

8969

审稿时长

1.6 months

期刊介绍： Chinese Chemical Letters (CCL) (ISSN 1001-8417) was founded in July 1990. The journal publishes preliminary accounts in the whole field of chemistry, including inorganic chemistry, organic chemistry, analytical chemistry, physical chemistry, polymer chemistry, applied chemistry, etc.Chinese Chemical Letters does not accept articles previously published or scheduled to be published. To verify originality, your article may be checked by the originality detection service CrossCheck.