Katelyn M. Clutterbuck, Hunter J. Windsor, Deanna M. D'Alessandro and Girish Lakhwani
{"title":"樟脑酸盐基手性金属-有机骨架的光开关热响应","authors":"Katelyn M. Clutterbuck, Hunter J. Windsor, Deanna M. D'Alessandro and Girish Lakhwani","doi":"10.1039/D5DT00814J","DOIUrl":null,"url":null,"abstract":"<p >Photoswitchable chiral materials are highly sought for various applications, including sensing, nonlinear optics, and liquid-crystalline devices. However, the origin and control of switching have not been well studied. Here, we report two chiral naphthalene diimide (NDI)-based Metal Organic Framework (MOF) materials, [Zn<small><sub>4</sub></small>(cam)<small><sub>4</sub></small>(DPNDI)<small><sub>2</sub></small>]·3DMF (<strong>Zn-MOF</strong>) (cam<small><sup>2−</sup></small> = camphorate, DPNDI = <em>N</em>,<em>N</em>′-di(4-pyridyl)-1,4,5,8-naphthalenetetracarboxydiimide) and [Cd<small><sub>4</sub></small>(cam)<small><sub>4</sub></small>(DPNDI)<small><sub>4</sub></small>]·3EtOH·5DMF (<strong>Cd-MOF</strong>) that undergo a photoinduced reduction of the NDI cores. Delocalisation of the generated mixed-valence state in <strong>Cd-MOF</strong> stabilises the radical state and alters its response in comparison to <strong>Zn-MOF</strong>. The photoinduced reduction reveals a reversible change in the sign of the circular dichroism spectrum of <strong>Cd-MOF</strong>. These materials show promise in understanding and controlling chiroptical materials for next-generation devices.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" 28","pages":" 11089-11094"},"PeriodicalIF":3.3000,"publicationDate":"2025-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Photoswitching chiroptical response in camphorate-based chiral metal–organic frameworks†\",\"authors\":\"Katelyn M. Clutterbuck, Hunter J. Windsor, Deanna M. D'Alessandro and Girish Lakhwani\",\"doi\":\"10.1039/D5DT00814J\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Photoswitchable chiral materials are highly sought for various applications, including sensing, nonlinear optics, and liquid-crystalline devices. However, the origin and control of switching have not been well studied. Here, we report two chiral naphthalene diimide (NDI)-based Metal Organic Framework (MOF) materials, [Zn<small><sub>4</sub></small>(cam)<small><sub>4</sub></small>(DPNDI)<small><sub>2</sub></small>]·3DMF (<strong>Zn-MOF</strong>) (cam<small><sup>2−</sup></small> = camphorate, DPNDI = <em>N</em>,<em>N</em>′-di(4-pyridyl)-1,4,5,8-naphthalenetetracarboxydiimide) and [Cd<small><sub>4</sub></small>(cam)<small><sub>4</sub></small>(DPNDI)<small><sub>4</sub></small>]·3EtOH·5DMF (<strong>Cd-MOF</strong>) that undergo a photoinduced reduction of the NDI cores. Delocalisation of the generated mixed-valence state in <strong>Cd-MOF</strong> stabilises the radical state and alters its response in comparison to <strong>Zn-MOF</strong>. The photoinduced reduction reveals a reversible change in the sign of the circular dichroism spectrum of <strong>Cd-MOF</strong>. These materials show promise in understanding and controlling chiroptical materials for next-generation devices.</p>\",\"PeriodicalId\":71,\"journal\":{\"name\":\"Dalton Transactions\",\"volume\":\" 28\",\"pages\":\" 11089-11094\"},\"PeriodicalIF\":3.3000,\"publicationDate\":\"2025-06-24\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Dalton Transactions\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.rsc.org/en/content/articlelanding/2025/dt/d5dt00814j\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Dalton Transactions","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2025/dt/d5dt00814j","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Photoswitching chiroptical response in camphorate-based chiral metal–organic frameworks†
Photoswitchable chiral materials are highly sought for various applications, including sensing, nonlinear optics, and liquid-crystalline devices. However, the origin and control of switching have not been well studied. Here, we report two chiral naphthalene diimide (NDI)-based Metal Organic Framework (MOF) materials, [Zn4(cam)4(DPNDI)2]·3DMF (Zn-MOF) (cam2− = camphorate, DPNDI = N,N′-di(4-pyridyl)-1,4,5,8-naphthalenetetracarboxydiimide) and [Cd4(cam)4(DPNDI)4]·3EtOH·5DMF (Cd-MOF) that undergo a photoinduced reduction of the NDI cores. Delocalisation of the generated mixed-valence state in Cd-MOF stabilises the radical state and alters its response in comparison to Zn-MOF. The photoinduced reduction reveals a reversible change in the sign of the circular dichroism spectrum of Cd-MOF. These materials show promise in understanding and controlling chiroptical materials for next-generation devices.
期刊介绍:
Dalton Transactions is a journal for all areas of inorganic chemistry, which encompasses the organometallic, bioinorganic and materials chemistry of the elements, with applications including synthesis, catalysis, energy conversion/storage, electrical devices and medicine. Dalton Transactions welcomes high-quality, original submissions in all of these areas and more, where the advancement of knowledge in inorganic chemistry is significant.