Oxime-functionalized [Ir(C1^N1)(C2^N2)(O^O)]-tris-heteroleptic Ir(III)-complex towards efficient near-infrared (NIR) phosphorescence and singlet oxygen generation

IF 3.6 3区物理与天体物理 Q2 OPTICS

Journal of Luminescence Pub Date : 2025-09-16 DOI:10.1016/j.jlumin.2025.121550

Hanqian Meng , Yan Zhang , Qinglin Chen , Youquan Chen , Sicheng Yao , Guorui Fu , Yongquan Wu , Lingmin Pei , Xingqiang Lü

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引用次数: 0

Abstract

The development of efficient near-infrared (NIR) photosensitizer based on the Ir(III)-complexes is highly challenging due to the limitation of the “energy gap law”. In this work, we successfully developed a novel oxime-functionalized tris-heteroleptic Ir(III)-complex [Ir(iqbt)(pbao)(acac)] (2) with excellent NIR-luminescence (λ_em^Max = 719 nm and Φ_PL = 2.3 %) via the post-modification from the precursor [Ir(iqbt)(pba)(acac)] (1). Intriguingly, besides the augmented ³MLCT effect, the large efficiency (2.3 %) should be further beneficial from the suppressed non-radiative deactivation with the terminal oxime group in a restrictive E conformation. Moreover, the oxime-functionalized Ir(III)-complex 2 was demonstrated to have high singlet oxygen (¹O₂) quantum efficiency of 0.56, minimal dark cytotoxicity while distinct phototoxicity (IC₅₀ value = 5.55 μM), against MCF-7 human breast cancer cells.

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肟功能化[Ir(C1^N1)(C2^N2)(O^O)]-三杂电性Ir（III）配合物对近红外（NIR）磷光和单线态产氧的影响

由于“能隙定律”的限制，基于Ir（III）配合物的高效近红外（NIR）光敏剂的开发极具挑战性。在这项工作中，我们通过前体[Ir(iqbt)(pba)(acac)](1)的后修饰，成功地开发了一种新的肟功能化三异电性Ir（III）配合物[Ir(iqbt)(pbao)(acac)](2)，具有优异的nir发光（λemMax = 719 nm， ΦPL = 2.3%）。有趣的是，除了增强的3MLCT效应，高效率（2.3%）应该进一步得益于抑制非辐射失活与末端肟基在限制性E构象。此外，肟功能化的Ir(III)-配合物2对MCF-7人乳腺癌细胞具有0.56的单线态氧（1O2）量子效率，具有最小的暗细胞毒性和光毒性（IC50值= 5.55 μM）。

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来源期刊

Journal of Luminescence 物理-光学

CiteScore

6.70

自引率

13.90%

发文量

850

审稿时长

3.8 months

期刊介绍： The purpose of the Journal of Luminescence is to provide a means of communication between scientists in different disciplines who share a common interest in the electronic excited states of molecular, ionic and covalent systems, whether crystalline, amorphous, or liquid. We invite original papers and reviews on such subjects as: exciton and polariton dynamics, dynamics of localized excited states, energy and charge transport in ordered and disordered systems, radiative and non-radiative recombination, relaxation processes, vibronic interactions in electronic excited states, photochemistry in condensed systems, excited state resonance, double resonance, spin dynamics, selective excitation spectroscopy, hole burning, coherent processes in excited states, (e.g. coherent optical transients, photon echoes, transient gratings), multiphoton processes, optical bistability, photochromism, and new techniques for the study of excited states. This list is not intended to be exhaustive. Papers in the traditional areas of optical spectroscopy (absorption, MCD, luminescence, Raman scattering) are welcome. Papers on applications (phosphors, scintillators, electro- and cathodo-luminescence, radiography, bioimaging, solar energy, energy conversion, etc.) are also welcome if they present results of scientific, rather than only technological interest. However, papers containing purely theoretical results, not related to phenomena in the excited states, as well as papers using luminescence spectroscopy to perform routine analytical chemistry or biochemistry procedures, are outside the scope of the journal. Some exceptions will be possible at the discretion of the editors.