Dijo Prasannan, Yuriy V Zatsikha, Victor N Nemykin
{"title":"吡啶附加MB-DIPYs的自由基和氧化还原形式。","authors":"Dijo Prasannan, Yuriy V Zatsikha, Victor N Nemykin","doi":"10.1002/asia.202500694","DOIUrl":null,"url":null,"abstract":"<p><p>We discuss the synthesis and properties of pyridine-appended nickel(II) complex of \"Manitoba dipyrromethene\" (Ni<sup>II</sup>(MB-DIPY)), which is stable radical at ambient conditions. The Ni<sup>II</sup>(MB-DIPY), 6<sup>•</sup> shows absorption at ∼1300 nm and a g-value of ∼2.00 in EPR. The redox features of Ni<sup>II</sup>(MB-DIPY) were studied by electro- and spectroelectrochemistry. The reduced form, 6<sup>-</sup>, has an intense NIR absorption and a broad spectrum in the visible region, making this compound a prospective non-fullerene acceptor for light-harvesting. The axial coordination and photophysical properties of the supramolecular dyad formed between pyridine-appended Ni<sup>II</sup>(MB-DIPY) with zinc 5,10,15,20-tetrakis-(pentafluorophenyl)porphyrin (TPP<sup>F20</sup>Zn) were also studied. Ni<sup>II</sup>(MB-DIPY) 6<sup>•</sup> failed to interact with TPP<sup>F20</sup>Zn. However, reduced Ni<sup>II</sup>(MB-DIPY) in its anionic form, 6<sup>-</sup>, self-assembles and forms a donor-acceptor dyad with TPP<sup>F20</sup>Zn with a binding constant of K<sub>a</sub> = 1.13 × 10<sup>2</sup> M<sup>-1</sup> and fluorescence quenching constant of K<sub>SV</sub> = 1.31 × 10<sup>3</sup> M<sup>-1</sup>. This work represents the first report on the potential of MB-DIPYs to self-assemble and form a donor-acceptor type supramolecular dyad with TPP<sup>F20</sup>Zn. This study explored the potential of the MB-DIPYs to act as a non-fullerene acceptor in light-harvesting supramolecular donor-acceptor systems formed via non-covalent interactions.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e00694"},"PeriodicalIF":3.3000,"publicationDate":"2025-06-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Radical and Redox Forms of Pyridyl Appended MB-DIPYs.\",\"authors\":\"Dijo Prasannan, Yuriy V Zatsikha, Victor N Nemykin\",\"doi\":\"10.1002/asia.202500694\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>We discuss the synthesis and properties of pyridine-appended nickel(II) complex of \\\"Manitoba dipyrromethene\\\" (Ni<sup>II</sup>(MB-DIPY)), which is stable radical at ambient conditions. The Ni<sup>II</sup>(MB-DIPY), 6<sup>•</sup> shows absorption at ∼1300 nm and a g-value of ∼2.00 in EPR. The redox features of Ni<sup>II</sup>(MB-DIPY) were studied by electro- and spectroelectrochemistry. The reduced form, 6<sup>-</sup>, has an intense NIR absorption and a broad spectrum in the visible region, making this compound a prospective non-fullerene acceptor for light-harvesting. The axial coordination and photophysical properties of the supramolecular dyad formed between pyridine-appended Ni<sup>II</sup>(MB-DIPY) with zinc 5,10,15,20-tetrakis-(pentafluorophenyl)porphyrin (TPP<sup>F20</sup>Zn) were also studied. Ni<sup>II</sup>(MB-DIPY) 6<sup>•</sup> failed to interact with TPP<sup>F20</sup>Zn. However, reduced Ni<sup>II</sup>(MB-DIPY) in its anionic form, 6<sup>-</sup>, self-assembles and forms a donor-acceptor dyad with TPP<sup>F20</sup>Zn with a binding constant of K<sub>a</sub> = 1.13 × 10<sup>2</sup> M<sup>-1</sup> and fluorescence quenching constant of K<sub>SV</sub> = 1.31 × 10<sup>3</sup> M<sup>-1</sup>. This work represents the first report on the potential of MB-DIPYs to self-assemble and form a donor-acceptor type supramolecular dyad with TPP<sup>F20</sup>Zn. This study explored the potential of the MB-DIPYs to act as a non-fullerene acceptor in light-harvesting supramolecular donor-acceptor systems formed via non-covalent interactions.</p>\",\"PeriodicalId\":145,\"journal\":{\"name\":\"Chemistry - An Asian Journal\",\"volume\":\" \",\"pages\":\"e00694\"},\"PeriodicalIF\":3.3000,\"publicationDate\":\"2025-06-17\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Chemistry - An Asian Journal\",\"FirstCategoryId\":\"1\",\"ListUrlMain\":\"https://doi.org/10.1002/asia.202500694\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemistry - An Asian Journal","FirstCategoryId":"1","ListUrlMain":"https://doi.org/10.1002/asia.202500694","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Radical and Redox Forms of Pyridyl Appended MB-DIPYs.
We discuss the synthesis and properties of pyridine-appended nickel(II) complex of "Manitoba dipyrromethene" (NiII(MB-DIPY)), which is stable radical at ambient conditions. The NiII(MB-DIPY), 6• shows absorption at ∼1300 nm and a g-value of ∼2.00 in EPR. The redox features of NiII(MB-DIPY) were studied by electro- and spectroelectrochemistry. The reduced form, 6-, has an intense NIR absorption and a broad spectrum in the visible region, making this compound a prospective non-fullerene acceptor for light-harvesting. The axial coordination and photophysical properties of the supramolecular dyad formed between pyridine-appended NiII(MB-DIPY) with zinc 5,10,15,20-tetrakis-(pentafluorophenyl)porphyrin (TPPF20Zn) were also studied. NiII(MB-DIPY) 6• failed to interact with TPPF20Zn. However, reduced NiII(MB-DIPY) in its anionic form, 6-, self-assembles and forms a donor-acceptor dyad with TPPF20Zn with a binding constant of Ka = 1.13 × 102 M-1 and fluorescence quenching constant of KSV = 1.31 × 103 M-1. This work represents the first report on the potential of MB-DIPYs to self-assemble and form a donor-acceptor type supramolecular dyad with TPPF20Zn. This study explored the potential of the MB-DIPYs to act as a non-fullerene acceptor in light-harvesting supramolecular donor-acceptor systems formed via non-covalent interactions.
期刊介绍:
Chemistry—An Asian Journal is an international high-impact journal for chemistry in its broadest sense. The journal covers all aspects of chemistry from biochemistry through organic and inorganic chemistry to physical chemistry, including interdisciplinary topics.
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