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":"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}
引用次数: 0
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.
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.