Justin Cado, Alexandre Abhervé*, Maxime Grasser, Nicolas Vanthuyne, Francesco Zinna, Lorenzo Di Bari, Boris Le Guennic* and Narcis Avarvari*,
{"title":"天然(+)-樟脑基双(吡唑基)吡啶铕(III)配合物的区域异构体诱导圆极化发光开关","authors":"Justin Cado, Alexandre Abhervé*, Maxime Grasser, Nicolas Vanthuyne, Francesco Zinna, Lorenzo Di Bari, Boris Le Guennic* and Narcis Avarvari*, ","doi":"10.1021/acs.inorgchem.5c01706","DOIUrl":null,"url":null,"abstract":"<p >Chiral 2,6-bis(pyrazol-1-yl)pyridine (bpp) ligands containing camphor units have been used in their enantiopure, racemic, and meso forms to prepare luminescent europium(III) complexes. The bpp ligands have been fully characterized by single-crystal X-ray diffraction and chiroptical spectroscopy. For one of the enantiopure ligands, namely bis(4<i>S</i>,7<i>R</i>)camphor-2,2-bpp, the regioisomer bis(4<i>S</i>,7<i>R</i>)camphor-1,2-bpp, containing one pyrazole connected through the N1 nitrogen atom, has been obtained and used to coordinate the europium(III) ion. Ancillary hexafluoroacetylacetonato ligands were used to complete the coordination sphere of the lanthanide. The complexes with the 2,2-bpp ligands have been structurally characterized by single-crystal X-ray diffraction. They are isostructural in spite of the noncentrosymmetric monoclinic <i>P</i>2<sub>1</sub> space group for the enantiopure compounds and the centrosymmetric monoclinic <i>P</i>2<sub>1</sub>/<i>n</i> space group for the meso and the racemic ones. The metal center is ennea-coordinated within slightly distorted Muffin-type geometry. The three enantiopure complexes show strong circularly polarized luminescence activity, with anisotropy factors <i>g</i><sub>lum</sub> reaching up ±0.2 for the <sup>7</sup>F<sub>1</sub> ← <sup>5</sup>D<sub>0</sub> magnetic dipole sensitive transition. Most remarkably, the polarization of the emission is inverted for the two complexes bearing the regioisomeric bis(4<i>S</i>,7<i>R</i>)camphor-2,2-bpp and bis(4<i>S</i>,7<i>R</i>)camphor-1,2-bpp ligands, yet having the same absolute configuration of the camphor units, thus allowing an unprecedented possibility of CPL switching.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"64 25","pages":"12781–12791"},"PeriodicalIF":4.7000,"publicationDate":"2025-06-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Regioisomerism Induced Circularly Polarized Luminescence Switching in Natural (+)-Camphor-Based Bis(pyrazolyl)pyridine Europium(III) Complexes\",\"authors\":\"Justin Cado, Alexandre Abhervé*, Maxime Grasser, Nicolas Vanthuyne, Francesco Zinna, Lorenzo Di Bari, Boris Le Guennic* and Narcis Avarvari*, \",\"doi\":\"10.1021/acs.inorgchem.5c01706\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Chiral 2,6-bis(pyrazol-1-yl)pyridine (bpp) ligands containing camphor units have been used in their enantiopure, racemic, and meso forms to prepare luminescent europium(III) complexes. The bpp ligands have been fully characterized by single-crystal X-ray diffraction and chiroptical spectroscopy. For one of the enantiopure ligands, namely bis(4<i>S</i>,7<i>R</i>)camphor-2,2-bpp, the regioisomer bis(4<i>S</i>,7<i>R</i>)camphor-1,2-bpp, containing one pyrazole connected through the N1 nitrogen atom, has been obtained and used to coordinate the europium(III) ion. Ancillary hexafluoroacetylacetonato ligands were used to complete the coordination sphere of the lanthanide. The complexes with the 2,2-bpp ligands have been structurally characterized by single-crystal X-ray diffraction. They are isostructural in spite of the noncentrosymmetric monoclinic <i>P</i>2<sub>1</sub> space group for the enantiopure compounds and the centrosymmetric monoclinic <i>P</i>2<sub>1</sub>/<i>n</i> space group for the meso and the racemic ones. The metal center is ennea-coordinated within slightly distorted Muffin-type geometry. The three enantiopure complexes show strong circularly polarized luminescence activity, with anisotropy factors <i>g</i><sub>lum</sub> reaching up ±0.2 for the <sup>7</sup>F<sub>1</sub> ← <sup>5</sup>D<sub>0</sub> magnetic dipole sensitive transition. Most remarkably, the polarization of the emission is inverted for the two complexes bearing the regioisomeric bis(4<i>S</i>,7<i>R</i>)camphor-2,2-bpp and bis(4<i>S</i>,7<i>R</i>)camphor-1,2-bpp ligands, yet having the same absolute configuration of the camphor units, thus allowing an unprecedented possibility of CPL switching.</p>\",\"PeriodicalId\":40,\"journal\":{\"name\":\"Inorganic Chemistry\",\"volume\":\"64 25\",\"pages\":\"12781–12791\"},\"PeriodicalIF\":4.7000,\"publicationDate\":\"2025-06-13\",\"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.5c01706\",\"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.5c01706","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Chiral 2,6-bis(pyrazol-1-yl)pyridine (bpp) ligands containing camphor units have been used in their enantiopure, racemic, and meso forms to prepare luminescent europium(III) complexes. The bpp ligands have been fully characterized by single-crystal X-ray diffraction and chiroptical spectroscopy. For one of the enantiopure ligands, namely bis(4S,7R)camphor-2,2-bpp, the regioisomer bis(4S,7R)camphor-1,2-bpp, containing one pyrazole connected through the N1 nitrogen atom, has been obtained and used to coordinate the europium(III) ion. Ancillary hexafluoroacetylacetonato ligands were used to complete the coordination sphere of the lanthanide. The complexes with the 2,2-bpp ligands have been structurally characterized by single-crystal X-ray diffraction. They are isostructural in spite of the noncentrosymmetric monoclinic P21 space group for the enantiopure compounds and the centrosymmetric monoclinic P21/n space group for the meso and the racemic ones. The metal center is ennea-coordinated within slightly distorted Muffin-type geometry. The three enantiopure complexes show strong circularly polarized luminescence activity, with anisotropy factors glum reaching up ±0.2 for the 7F1 ← 5D0 magnetic dipole sensitive transition. Most remarkably, the polarization of the emission is inverted for the two complexes bearing the regioisomeric bis(4S,7R)camphor-2,2-bpp and bis(4S,7R)camphor-1,2-bpp ligands, yet having the same absolute configuration of the camphor units, thus allowing an unprecedented possibility of CPL switching.
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.