Diamantoula Maniaki, Annika Sickinger, LEONI ALEJANDRA ALEJANDRA BARRIOS MORENO, David Aguilà, Olivier Roubeau, Yannick Guyot, François Riobé, Olivier Maury, Laura Abad Galan, Guillem Aromi
{"title":"分子复合物中 Nd3+ 和 Er3+ 中心之间的能量交换","authors":"Diamantoula Maniaki, Annika Sickinger, LEONI ALEJANDRA ALEJANDRA BARRIOS MORENO, David Aguilà, Olivier Roubeau, Yannick Guyot, François Riobé, Olivier Maury, Laura Abad Galan, Guillem Aromi","doi":"10.1039/d4sc03994g","DOIUrl":null,"url":null,"abstract":"The controlled and reproducible molecular assemblies incorporating lanthanide centers represents a crucial step in driving forward up- and down-conversion processes. This challenge calls for the development of strategies to facilitate the efficient in-situ segregation of different Ln metal ions into distinct positions within the molecule. The unique family of pure [LnLn′Ln] heterometallic coordination compounds previously developed by us represents an ideal platform for studying the desired Ln-to-Ln′ energy transfer (ET). In this context, we report here the new pure one-step synthetically produced [ErNdEr] (3) complex, which allows for the first time at the molecular level to study the mechanisms behind Nd-to-Er energy transfer. To further assess the photophysical properties of this complex, the analogous [LuNdLu] (1) and [ErLaEr] (2) complexes have been also prepared and photophysically studied. Efficient sensitization via the two β-diketones employed as main ligands was proben for both Nd3+ and Er3+ ions, resulting in highly resolved emission spectra and sufficiently long excited state lifetimes, which allowed to further assess the Ln-to-Ln′ ET. This intermetallic transfer was first detected by comparing the emission spectra of iso-absorbant solutions and demonstrated by comparing the lifetime values with or without the lanthanide quencher (Er3+), as well as with a deep analysis of the excitation spectrum of the three complexes. Thus, a very unique phenomenon was discovered, consisting in a mutual Nd-to-Er and Er-to-Nd ET with no net increase of brightness by any metal ; while Nd3+ transfers the energy received from the antena to Er3+, the sensitization of the latter results into back-transfer to Nd3+ to a non-emissive, thus silent state.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":null,"pages":null},"PeriodicalIF":7.6000,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Energy exchange between Nd3+ and Er3+ centers within molecular complexes\",\"authors\":\"Diamantoula Maniaki, Annika Sickinger, LEONI ALEJANDRA ALEJANDRA BARRIOS MORENO, David Aguilà, Olivier Roubeau, Yannick Guyot, François Riobé, Olivier Maury, Laura Abad Galan, Guillem Aromi\",\"doi\":\"10.1039/d4sc03994g\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"The controlled and reproducible molecular assemblies incorporating lanthanide centers represents a crucial step in driving forward up- and down-conversion processes. This challenge calls for the development of strategies to facilitate the efficient in-situ segregation of different Ln metal ions into distinct positions within the molecule. The unique family of pure [LnLn′Ln] heterometallic coordination compounds previously developed by us represents an ideal platform for studying the desired Ln-to-Ln′ energy transfer (ET). In this context, we report here the new pure one-step synthetically produced [ErNdEr] (3) complex, which allows for the first time at the molecular level to study the mechanisms behind Nd-to-Er energy transfer. To further assess the photophysical properties of this complex, the analogous [LuNdLu] (1) and [ErLaEr] (2) complexes have been also prepared and photophysically studied. Efficient sensitization via the two β-diketones employed as main ligands was proben for both Nd3+ and Er3+ ions, resulting in highly resolved emission spectra and sufficiently long excited state lifetimes, which allowed to further assess the Ln-to-Ln′ ET. This intermetallic transfer was first detected by comparing the emission spectra of iso-absorbant solutions and demonstrated by comparing the lifetime values with or without the lanthanide quencher (Er3+), as well as with a deep analysis of the excitation spectrum of the three complexes. Thus, a very unique phenomenon was discovered, consisting in a mutual Nd-to-Er and Er-to-Nd ET with no net increase of brightness by any metal ; while Nd3+ transfers the energy received from the antena to Er3+, the sensitization of the latter results into back-transfer to Nd3+ to a non-emissive, thus silent state.\",\"PeriodicalId\":9909,\"journal\":{\"name\":\"Chemical Science\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":7.6000,\"publicationDate\":\"2024-10-18\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Chemical Science\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1039/d4sc03994g\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemical Science","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1039/d4sc03994g","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Energy exchange between Nd3+ and Er3+ centers within molecular complexes
The controlled and reproducible molecular assemblies incorporating lanthanide centers represents a crucial step in driving forward up- and down-conversion processes. This challenge calls for the development of strategies to facilitate the efficient in-situ segregation of different Ln metal ions into distinct positions within the molecule. The unique family of pure [LnLn′Ln] heterometallic coordination compounds previously developed by us represents an ideal platform for studying the desired Ln-to-Ln′ energy transfer (ET). In this context, we report here the new pure one-step synthetically produced [ErNdEr] (3) complex, which allows for the first time at the molecular level to study the mechanisms behind Nd-to-Er energy transfer. To further assess the photophysical properties of this complex, the analogous [LuNdLu] (1) and [ErLaEr] (2) complexes have been also prepared and photophysically studied. Efficient sensitization via the two β-diketones employed as main ligands was proben for both Nd3+ and Er3+ ions, resulting in highly resolved emission spectra and sufficiently long excited state lifetimes, which allowed to further assess the Ln-to-Ln′ ET. This intermetallic transfer was first detected by comparing the emission spectra of iso-absorbant solutions and demonstrated by comparing the lifetime values with or without the lanthanide quencher (Er3+), as well as with a deep analysis of the excitation spectrum of the three complexes. Thus, a very unique phenomenon was discovered, consisting in a mutual Nd-to-Er and Er-to-Nd ET with no net increase of brightness by any metal ; while Nd3+ transfers the energy received from the antena to Er3+, the sensitization of the latter results into back-transfer to Nd3+ to a non-emissive, thus silent state.
期刊介绍:
Chemical Science is a journal that encompasses various disciplines within the chemical sciences. Its scope includes publishing ground-breaking research with significant implications for its respective field, as well as appealing to a wider audience in related areas. To be considered for publication, articles must showcase innovative and original advances in their field of study and be presented in a manner that is understandable to scientists from diverse backgrounds. However, the journal generally does not publish highly specialized research.