{"title":"氢键供体调控双核Cu(I)配合物的激发响应发光特性。","authors":"Hai-Jian Li, , , Li-Ping Lin, , , Jin-Wang Liu, , , Li-Hua He, , , Sui-Jun Liu, , , He-Rui Wen, , , Jian Zhao, , , Li You*, , and , Jing-Lin Chen*, ","doi":"10.1021/acs.inorgchem.5c02866","DOIUrl":null,"url":null,"abstract":"<p >The selection of hydrogen-bonding donors is crucial for the development of stimuli-responsive luminescent materials that rely on weak hydrogen-bonding interactions. In this study, we report two novel dinuclear Cu(I) complexes, [Cu<sub>2</sub>(μ-η<sup>2</sup>(<i>N</i>,<i>N</i>),η<sup>2</sup>(<i>N</i>,<i>N</i>)-dpa)(μ-dppm)<sub>2</sub>](ClO<sub>4</sub>) (<b>1</b>) and [Cu<sub>2</sub>(μ-η<sup>2</sup>(<i>N</i>,<i>N</i>),η<sup>2</sup>(<i>N</i>,<i>N</i>)-dpa)(μ-dppa)<sub>2</sub>](ClO<sub>4</sub>)·2CH<sub>3</sub>COCH<sub>3</sub> (<b>2</b>), which differ in their diphosphine linkers (CH<sub>2</sub> in dppm vs NH in dppa). X-ray crystallography reveals weak CH···O hydrogen bonds between dppm-CH<sub>2</sub> and perchlorate-O in <b>1</b> and weak NH···O interactions between dppa-NH and acetone-O in <b>2</b>. The destruction of CH···OClO<sub>3</sub><sup>–</sup> hydrogen bonds in <b>1</b>, induced by grinding, triggers mechanochromic luminescence. In <b>2</b>, the disruption of NH···OC(CH<sub>3</sub>)<sub>2</sub> hydrogen bonds, caused by heating and grinding, leads to both thermochromic and mechanochromic luminescence. It is demonstrated that differences in donor–acceptor pairing (CH<sub>2</sub>/ClO<sub>4</sub><sup>–</sup> vs NH/acetone) influence the nature and responsiveness of hydrogen-bonding interactions. Furthermore, these results offer new insights into the design and synthesis of low-cost, multistimuli-responsive luminescent materials through the modification of hydrogen-bonding donors.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"64 37","pages":"18892–18900"},"PeriodicalIF":4.7000,"publicationDate":"2025-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Stimuli-Responsive Luminescent Properties of Dinuclear Cu(I) Complexes Regulated by Hydrogen-Bonding Donors\",\"authors\":\"Hai-Jian Li, , , Li-Ping Lin, , , Jin-Wang Liu, , , Li-Hua He, , , Sui-Jun Liu, , , He-Rui Wen, , , Jian Zhao, , , Li You*, , and , Jing-Lin Chen*, \",\"doi\":\"10.1021/acs.inorgchem.5c02866\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >The selection of hydrogen-bonding donors is crucial for the development of stimuli-responsive luminescent materials that rely on weak hydrogen-bonding interactions. In this study, we report two novel dinuclear Cu(I) complexes, [Cu<sub>2</sub>(μ-η<sup>2</sup>(<i>N</i>,<i>N</i>),η<sup>2</sup>(<i>N</i>,<i>N</i>)-dpa)(μ-dppm)<sub>2</sub>](ClO<sub>4</sub>) (<b>1</b>) and [Cu<sub>2</sub>(μ-η<sup>2</sup>(<i>N</i>,<i>N</i>),η<sup>2</sup>(<i>N</i>,<i>N</i>)-dpa)(μ-dppa)<sub>2</sub>](ClO<sub>4</sub>)·2CH<sub>3</sub>COCH<sub>3</sub> (<b>2</b>), which differ in their diphosphine linkers (CH<sub>2</sub> in dppm vs NH in dppa). X-ray crystallography reveals weak CH···O hydrogen bonds between dppm-CH<sub>2</sub> and perchlorate-O in <b>1</b> and weak NH···O interactions between dppa-NH and acetone-O in <b>2</b>. The destruction of CH···OClO<sub>3</sub><sup>–</sup> hydrogen bonds in <b>1</b>, induced by grinding, triggers mechanochromic luminescence. In <b>2</b>, the disruption of NH···OC(CH<sub>3</sub>)<sub>2</sub> hydrogen bonds, caused by heating and grinding, leads to both thermochromic and mechanochromic luminescence. It is demonstrated that differences in donor–acceptor pairing (CH<sub>2</sub>/ClO<sub>4</sub><sup>–</sup> vs NH/acetone) influence the nature and responsiveness of hydrogen-bonding interactions. Furthermore, these results offer new insights into the design and synthesis of low-cost, multistimuli-responsive luminescent materials through the modification of hydrogen-bonding donors.</p>\",\"PeriodicalId\":40,\"journal\":{\"name\":\"Inorganic Chemistry\",\"volume\":\"64 37\",\"pages\":\"18892–18900\"},\"PeriodicalIF\":4.7000,\"publicationDate\":\"2025-09-08\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Inorganic Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.inorgchem.5c02866\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Inorganic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.inorgchem.5c02866","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
摘要
氢键供体的选择对于依赖弱氢键相互作用的刺激响应发光材料的开发至关重要。在这项研究中，我们报道了两种新的双核Cu(I)配合物[Cu2(μ-η2(N，N),η2(N，N)-dpa)(μ-dppm)2](ClO4)(1)和[Cu2(μ-η2(N，N) -dpa)(μ-dppa)2]（ClO4）·2CH3COCH3(2)，它们的二膦连接体（dppm中的CH2和dppa中的NH）不同。x射线晶体学显示dppm-CH2与1中的高氯酸盐-O之间存在弱CH··O氢键，dppa- nh2与2中的丙酮-O之间存在弱nhh··O相互作用。1中CH···OClO3-氢键被磨破，引发机械致变色发光。在2中，NH···OC(CH3)2氢键被加热和研磨破坏，导致热致变色和机械致变色发光。研究表明，供体-受体配对（CH2/ClO4- vs NH/丙酮）的差异会影响氢键相互作用的性质和响应性。此外，这些结果为通过修饰氢键供体来设计和合成低成本、多刺激响应的发光材料提供了新的见解。
Stimuli-Responsive Luminescent Properties of Dinuclear Cu(I) Complexes Regulated by Hydrogen-Bonding Donors
The selection of hydrogen-bonding donors is crucial for the development of stimuli-responsive luminescent materials that rely on weak hydrogen-bonding interactions. In this study, we report two novel dinuclear Cu(I) complexes, [Cu2(μ-η2(N,N),η2(N,N)-dpa)(μ-dppm)2](ClO4) (1) and [Cu2(μ-η2(N,N),η2(N,N)-dpa)(μ-dppa)2](ClO4)·2CH3COCH3 (2), which differ in their diphosphine linkers (CH2 in dppm vs NH in dppa). X-ray crystallography reveals weak CH···O hydrogen bonds between dppm-CH2 and perchlorate-O in 1 and weak NH···O interactions between dppa-NH and acetone-O in 2. The destruction of CH···OClO3– hydrogen bonds in 1, induced by grinding, triggers mechanochromic luminescence. In 2, the disruption of NH···OC(CH3)2 hydrogen bonds, caused by heating and grinding, leads to both thermochromic and mechanochromic luminescence. It is demonstrated that differences in donor–acceptor pairing (CH2/ClO4– vs NH/acetone) influence the nature and responsiveness of hydrogen-bonding interactions. Furthermore, these results offer new insights into the design and synthesis of low-cost, multistimuli-responsive luminescent materials through the modification of hydrogen-bonding donors.
期刊介绍：
Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.
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