Dooyoung Kim, Michael C. Rosko, Felix N. Castellano, Thomas G. Gray and Thomas S. Teets*,
{"title":"通过芘蜕变异氰酸酯的三重-三重能量转移实现三配位铜(I)配合物的长激发态寿命。","authors":"Dooyoung Kim, Michael C. Rosko, Felix N. Castellano, Thomas G. Gray and Thomas S. Teets*, ","doi":"10.1021/jacs.4c04288","DOIUrl":null,"url":null,"abstract":"<p >There has been much effort to improve excited-state lifetimes in photosensitizers based on earth-abundant first-row transition metals. Copper(I) complexes have gained significant attention in this field, and in most cases, sterically driven approaches are used to optimize their lifetimes. This study presents a series of three-coordinate copper(I) complexes (<b>Cu1</b>–<b>Cu3</b>) where the excited-state lifetime is extended by triplet–triplet energy transfer. The heteroleptic compounds feature a cyclohexyl-substituted β-diketiminate (CyNacNac<sup>Me</sup>) paired with aryl isocyanide ligands, giving the general formula Cu(CyNacNac<sup>Me</sup>)(CN-Ar) (CN-dmp = 2,6-dimethylphenyl isocyanide for <b>Cu1</b>; CN-pyr = 1-pyrenyl isocyanide for <b>Cu2</b>; CN-dmp-pyr = 2,6-dimethyl-4-(1-pyrenyl)phenyl isocyanide for <b>Cu3</b>). The nature, energies, and dynamics of the low-energy triplet excited states are assessed with a combination of photoluminescence measurements at room temperature and 77 K, ultrafast transient absorption (UFTA) spectroscopy, and DFT calculations. The complexes with the pyrene-decorated isocyanides (<b>Cu2</b> and <b>Cu3</b>) exhibit extended excited-state lifetimes resulting from triplet–triplet energy transfer (TTET) between the short-lived charge-transfer excited state (<sup>3</sup>CT) and the long-lived pyrene-centered triplet state (<sup>3</sup>pyr). This TTET process is irreversible in <b>Cu3</b>, producing exclusively the <sup>3</sup>pyr state, and in <b>Cu2</b>, the <sup>3</sup>CT and <sup>3</sup>pyr states are nearly isoenergetic, enabling reversible TTET and long-lived <sup>3</sup>CT luminescence. The improved photophysical properties in <b>Cu2</b> and <b>Cu3</b> result in improvements in activity for both photocatalytic stilbene <i>E</i>/<i>Z</i> isomerization via triplet energy transfer and photoredox transformations involving hydrodebromination and C–O bond activation. These results illustrate that the extended excited-state lifetimes achieved through TTET result in newly conceived photosynthetically relevant earth-abundant transition metal complexes.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":null,"pages":null},"PeriodicalIF":14.4000,"publicationDate":"2024-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Long Excited-State Lifetimes in Three-Coordinate Copper(I) Complexes via Triplet–Triplet Energy Transfer to Pyrene-Decorated Isocyanides\",\"authors\":\"Dooyoung Kim, Michael C. Rosko, Felix N. Castellano, Thomas G. Gray and Thomas S. Teets*, \",\"doi\":\"10.1021/jacs.4c04288\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >There has been much effort to improve excited-state lifetimes in photosensitizers based on earth-abundant first-row transition metals. Copper(I) complexes have gained significant attention in this field, and in most cases, sterically driven approaches are used to optimize their lifetimes. This study presents a series of three-coordinate copper(I) complexes (<b>Cu1</b>–<b>Cu3</b>) where the excited-state lifetime is extended by triplet–triplet energy transfer. The heteroleptic compounds feature a cyclohexyl-substituted β-diketiminate (CyNacNac<sup>Me</sup>) paired with aryl isocyanide ligands, giving the general formula Cu(CyNacNac<sup>Me</sup>)(CN-Ar) (CN-dmp = 2,6-dimethylphenyl isocyanide for <b>Cu1</b>; CN-pyr = 1-pyrenyl isocyanide for <b>Cu2</b>; CN-dmp-pyr = 2,6-dimethyl-4-(1-pyrenyl)phenyl isocyanide for <b>Cu3</b>). The nature, energies, and dynamics of the low-energy triplet excited states are assessed with a combination of photoluminescence measurements at room temperature and 77 K, ultrafast transient absorption (UFTA) spectroscopy, and DFT calculations. The complexes with the pyrene-decorated isocyanides (<b>Cu2</b> and <b>Cu3</b>) exhibit extended excited-state lifetimes resulting from triplet–triplet energy transfer (TTET) between the short-lived charge-transfer excited state (<sup>3</sup>CT) and the long-lived pyrene-centered triplet state (<sup>3</sup>pyr). This TTET process is irreversible in <b>Cu3</b>, producing exclusively the <sup>3</sup>pyr state, and in <b>Cu2</b>, the <sup>3</sup>CT and <sup>3</sup>pyr states are nearly isoenergetic, enabling reversible TTET and long-lived <sup>3</sup>CT luminescence. The improved photophysical properties in <b>Cu2</b> and <b>Cu3</b> result in improvements in activity for both photocatalytic stilbene <i>E</i>/<i>Z</i> isomerization via triplet energy transfer and photoredox transformations involving hydrodebromination and C–O bond activation. These results illustrate that the extended excited-state lifetimes achieved through TTET result in newly conceived photosynthetically relevant earth-abundant transition metal complexes.</p>\",\"PeriodicalId\":49,\"journal\":{\"name\":\"Journal of the American Chemical Society\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":14.4000,\"publicationDate\":\"2024-07-02\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of the American Chemical Society\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/jacs.4c04288\",\"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":"Journal of the American Chemical Society","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/jacs.4c04288","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Long Excited-State Lifetimes in Three-Coordinate Copper(I) Complexes via Triplet–Triplet Energy Transfer to Pyrene-Decorated Isocyanides
There has been much effort to improve excited-state lifetimes in photosensitizers based on earth-abundant first-row transition metals. Copper(I) complexes have gained significant attention in this field, and in most cases, sterically driven approaches are used to optimize their lifetimes. This study presents a series of three-coordinate copper(I) complexes (Cu1–Cu3) where the excited-state lifetime is extended by triplet–triplet energy transfer. The heteroleptic compounds feature a cyclohexyl-substituted β-diketiminate (CyNacNacMe) paired with aryl isocyanide ligands, giving the general formula Cu(CyNacNacMe)(CN-Ar) (CN-dmp = 2,6-dimethylphenyl isocyanide for Cu1; CN-pyr = 1-pyrenyl isocyanide for Cu2; CN-dmp-pyr = 2,6-dimethyl-4-(1-pyrenyl)phenyl isocyanide for Cu3). The nature, energies, and dynamics of the low-energy triplet excited states are assessed with a combination of photoluminescence measurements at room temperature and 77 K, ultrafast transient absorption (UFTA) spectroscopy, and DFT calculations. The complexes with the pyrene-decorated isocyanides (Cu2 and Cu3) exhibit extended excited-state lifetimes resulting from triplet–triplet energy transfer (TTET) between the short-lived charge-transfer excited state (3CT) and the long-lived pyrene-centered triplet state (3pyr). This TTET process is irreversible in Cu3, producing exclusively the 3pyr state, and in Cu2, the 3CT and 3pyr states are nearly isoenergetic, enabling reversible TTET and long-lived 3CT luminescence. The improved photophysical properties in Cu2 and Cu3 result in improvements in activity for both photocatalytic stilbene E/Z isomerization via triplet energy transfer and photoredox transformations involving hydrodebromination and C–O bond activation. These results illustrate that the extended excited-state lifetimes achieved through TTET result in newly conceived photosynthetically relevant earth-abundant transition metal complexes.
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