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含氮配体单核和多核光致发光铜（I）配合物的最新进展及其刺激响应性

Recent advances in mono- and multi-nuclear photoluminescent Cu(i) complexes with nitrogen containing ligands and their stimuli responsiveness.

作者信息

Forni Alessandra, Malpicci Daniele, Lucenti Elena, Zecchinello Luca, Colombo Alessia, Cariati Elena

机构信息

Institute of Chemical Sciences and Technologies ''Giulio Natta'' (SCITEC) of CNR Via Golgi 19 20133 Milano Italy.

Department of Chemistry, Università degli Studi di Milano Via Golgi 19 20133 Milano Italy

出版信息

Chem Sci. 2025 Oct 17;16(44):20755-20805. doi: 10.1039/d5sc04685h. eCollection 2025 Nov 12.

DOI:10.1039/d5sc04685h
PMID:41190187
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC12581026/
Abstract

Luminescent Cu(i)-derivatives represent a highly desirable alternative to their noble metal analogues in view of copper's relative abundance and low environmental concerns while maintaining large color tunability, high quantum yield and low photo-thermal lability. Moreover, the large variety of structural forms, spanning from 0D mononuclear to 3D polynuclear compounds characterized by peculiar emissive features, opens the door to an incredibly huge family of Cu(i) derivatives with potential application in many different fields. The present review focuses on luminescent neutral 0D mono-, di-, tri- and tetranuclear Cu(i) complexes with N-donor ligands developed during the period 2020 to mid-2025. After a general overview, specific sections are dedicated to members of each nuclearity. Emphasis is given to compounds' stimuli responsiveness, in particular towards vapour exposure and thermal and mechanical perturbations.

摘要

鉴于铜的相对丰富性和较低的环境影响，同时保持较大的颜色可调性、高量子产率和低光热不稳定性，发光铜（I）衍生物是其贵金属类似物非常理想的替代品。此外，从具有独特发射特性的零维单核到三维多核化合物的多种结构形式，为具有潜在应用于许多不同领域的庞大铜（I）衍生物家族打开了大门。本综述重点关注2020年至2025年年中开发的具有氮供体配体的发光中性零维单核、双核、三核和四核铜（I）配合物。在进行总体概述之后，特定部分专门介绍了每个核数的成员。重点关注化合物的刺激响应性，特别是对蒸汽暴露以及热和机械扰动的响应性。

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Matrix Sputtering Method: A Novel Physical Approach for Photoluminescent Noble Metal Nanoclusters.矩阵溅射法：一种新颖的物理方法用于制备光致发光贵金属纳米团簇。
Acc Chem Res. 2017 Dec 19;50(12):2986-2995. doi: 10.1021/acs.accounts.7b00470. Epub 2017 Nov 30.
6
TADF: Enabling luminescent copper(i) coordination compounds for light-emitting electrochemical cells.热活化延迟荧光：实现用于发光电化学电池的发光铜（I）配位化合物
J Mater Chem C Mater. 2021 Oct 12;10(12):4456-4482. doi: 10.1039/d1tc04028f. eCollection 2022 Mar 24.
7
Estrone-salicylaldehyde N-methylated thiosemicarbazone hybrids and their copper complexes: solution structure, stability and anticancer activity in tumour spheroids.雌酮-水杨醛 N-甲基硫代缩氨基脲杂化物及其铜配合物：在肿瘤球体中的溶液结构、稳定性和抗癌活性。
J Biol Inorg Chem. 2021 Oct;26(7):775-791. doi: 10.1007/s00775-021-01891-7. Epub 2021 Aug 28.
8
Mononuclear to polynuclear transition induced by ligand coordination: synthesis, X-ray structure, and properties of mono-, di-, and polynuclear copper(II) complexes of pyridyl-containing azo ligands.配体配位诱导的单核到多核转变：含吡啶基偶氮配体的单核、双核和多核铜（II）配合物的合成、X射线结构及性质
Inorg Chem. 2006 Jan 23;45(2):562-70. doi: 10.1021/ic051029c.
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A Series of Mixed-Ligand Cu(I) Complexes Comprising Diphosphine-Disulfide Ligands: Effects of Diphosphine Ligands on Luminescent Properties.一系列包含双膦二硫配体的混合配体 Cu(I) 配合物：双膦配体对发光性质的影响。
Inorg Chem. 2020 Sep 8;59(17):12375-12384. doi: 10.1021/acs.inorgchem.0c01445. Epub 2020 Aug 24.
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Di- and tetranuclear metal complexes with phenoxo bridges: synthesis, structures, and photoluminescent and electroluminescent properties.含苯氧基桥联的双核和四核金属配合物：合成、结构以及光致发光和电致发光性质
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Efficient Red Electroluminescent Copper Complexes with Fluorination-Balanced Dual Emission.具有氟化平衡双发射的高效红色电致发光铜配合物
Research (Wash D C). 2026 Jan 14;9:1088. doi: 10.34133/research.1088. eCollection 2026.

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Interplay of the Cu⋯Cu distance and coordination geometry as a factor affecting the quantum efficiency in dimeric copper(I) halide complexes with derivatives of 4-pyrazolylpyrimidine-2-thiol.二聚卤化亚铜配合物中铜⋯铜间距与配位几何结构的相互作用作为影响其量子效率的一个因素：以4-吡唑基嘧啶-2-硫醇衍生物为研究对象
Dalton Trans. 2025 Jun 3;54(22):9000-9015. doi: 10.1039/d5dt00498e.
2
Synthesis and Characterization of Copper(I) Halide Heteroleptic Complexes with Thermally Activated Delayed Fluorescence.具有热活化延迟荧光的卤化亚铜杂配络合物的合成与表征
Inorg Chem. 2025 Apr 28;64(16):8334-8342. doi: 10.1021/acs.inorgchem.5c00733. Epub 2025 Apr 16.
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Enabling Thermally Stimulated Delayed Phosphorescence in Cu(I) Cyclic Trinuclear Complexes with Near-Unity Quantum Yield.
在量子产率近乎为1的铜（I）环状三核配合物中实现热激发延迟磷光。
J Am Chem Soc. 2025 Feb 26;147(8):6415-6426. doi: 10.1021/jacs.4c09907. Epub 2025 Feb 17.
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Copper(I) Halide Complex Featuring Blue Thermally Activated Delayed Fluorescence and Aggregate Induced Emission for Efficient X-ray Scintillation and Imaging.具有蓝色热激活延迟荧光和聚集诱导发光特性的卤化亚铜配合物用于高效X射线闪烁和成像
Angew Chem Int Ed Engl. 2025 Apr 25;64(18):e202422995. doi: 10.1002/anie.202422995. Epub 2025 Feb 26.
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Afterglow Copper(I) Iodine Cluster Scintillator.余辉碘化亚铜簇闪烁体。
Angew Chem Int Ed Engl. 2025 Mar 24;64(13):e202500481. doi: 10.1002/anie.202500481. Epub 2025 Feb 21.
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Harnessing of Cooperative Cu⋅⋅⋅H Interactions for Luminescent Low-Coordinate Copper(I) Complexes towards Stable OLEDs.利用协同铜⋅⋅⋅氢相互作用制备用于稳定有机发光二极管的发光低配位铜（I）配合物。
Angew Chem Int Ed Engl. 2025 Feb 10;64(7):e202419290. doi: 10.1002/anie.202419290. Epub 2024 Dec 13.
7
Structural and Photophysical Differences in Crystalline Trigonal Planar Copper Iodide Complexes with 1,2-Bis(methylpyridin-2-yl)disilane Ligands.含1,2-双（甲基吡啶-2-基）乙硅烷配体的晶体三角平面碘化亚铜配合物的结构和光物理差异
Inorg Chem. 2024 Nov 25;63(47):22361-22371. doi: 10.1021/acs.inorgchem.4c02758. Epub 2024 Nov 8.
8
Rigidochromism of tetranuclear Cu(I)-pyrazolate macrocycles: steric crowding with trifluoromethyl groups.四核铜（I）-吡唑酸盐大环化合物的刚性变色：三氟甲基的空间拥挤效应
Chem Commun (Camb). 2024 Oct 3;60(80):11307-11310. doi: 10.1039/d4cc04259j.
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Luminescence Behavior of Cationic and Neutral Cu Complexes of Phosphine and Pyridine Embedded 1,2,3-Triazole.膦和吡啶嵌入的1,2,3-三唑的阳离子和中性铜配合物的发光行为
Inorg Chem. 2024 Sep 16;63(37):16981-16990. doi: 10.1021/acs.inorgchem.4c02586. Epub 2024 Sep 5.
10
Substituents' Effect on the Photophysics of Trinuclear Copper(I) and Silver(I) Pyrazolate-Phosphine Cages.取代基对三核铜（I）和银（I）吡唑啉-膦笼合物光物理性质的影响。
Inorg Chem. 2024 Sep 9;63(36):16610-16621. doi: 10.1021/acs.inorgchem.4c00751. Epub 2024 Aug 28.