Paige J Brown, Yunfan Qiu, Elisabeth I Latawiec, Brian T Phelan, Nikolai A Tcyrulnikov, Jonathan R Palmer, Matthew D Krzyaniak, Sebastian M Kopp, Yuheng Huang, Ryan M Young, Michael R Wasielewski
{"title":"增强供体-色团-受体系统中的光生自由基对特性,促进量子信息应用。","authors":"Paige J Brown, Yunfan Qiu, Elisabeth I Latawiec, Brian T Phelan, Nikolai A Tcyrulnikov, Jonathan R Palmer, Matthew D Krzyaniak, Sebastian M Kopp, Yuheng Huang, Ryan M Young, Michael R Wasielewski","doi":"10.1021/acs.jpca.4c05015","DOIUrl":null,"url":null,"abstract":"<p><p>We report on new donor-chromophore-acceptor triads <b>BDX-ANI-NDI</b> and <b>BDX-ANI-xy-NDI</b> where the BDX donor is 2,2,6,6-tetramethylbenzo[1,2-<i>d</i>;4,5-<i>d</i>]bis[1,3]dioxole, the ANI chromophore is 4-(<i>N</i>-piperidinyl)naphthalene-1,8-dicarboximide, the NDI acceptor is naphthalene-1,8:4,5-bis(dicarboximide), and xy is a 2,5-xylyl spacer. The results on these compounds are compared to the analogous derivatives having a <i>p</i>-methoxyaniline (MeOAn) as the donor. BDX<sup>•<b>+</b></sup> has no nitrogen atoms and only a single hydrogen atom coupled to its unpaired electron spin, and therefore has significantly decreased hyperfine interactions compared to MeOAn<sup><b>•+</b></sup>. We use femtosecond transient absorption (fsTA) and nanosecond TA (nsTA) spectroscopies, the latter with an applied static magnetic field, to study the charge transfer dynamics and determine the spin-spin exchange interaction (<i>J</i>) for <b>BDX</b><sup><b>•+</b></sup><b>-ANI-NDI</b><sup><b>•-</b></sup> and <b>BDX</b><sup><b>•+</b></sup><b>-ANI-xy-NDI</b><sup><b>•-</b></sup> at both ambient and cryogenic temperatures. Time-resolved electron paramagnetic resonance (EPR) and pulse-EPR measurements on these spin-correlated radical pairs (SCRPs) were used to probe their spin dynamics. We demonstrate that <b>BDX</b><sup><b>•+</b></sup><b>-ANI-xy-NDI</b><sup><b>•-</b></sup> has an unusually long lifetime of ∼550 μs in glassy butyronitrile (PrCN) at 85 K, which makes it useful for pulse-EPR studies that target quantum information science (QIS) applications. We also show that rotation of the BDX group about the single bond linking it to the neighboring phenyl group has a significant impact on the spin dynamics, and in particular the magnitude of <i>J</i>. By comparing the results on these compounds to the analogous MeOAn series, insights into design principles for creating improved spin-correlated radical pair systems for QIS studies are obtained.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":null,"pages":null},"PeriodicalIF":2.7000,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Enhancing Photogenerated Radical Pair Properties in Donor-Chromophore-Acceptor Systems for Quantum Information Applications.\",\"authors\":\"Paige J Brown, Yunfan Qiu, Elisabeth I Latawiec, Brian T Phelan, Nikolai A Tcyrulnikov, Jonathan R Palmer, Matthew D Krzyaniak, Sebastian M Kopp, Yuheng Huang, Ryan M Young, Michael R Wasielewski\",\"doi\":\"10.1021/acs.jpca.4c05015\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>We report on new donor-chromophore-acceptor triads <b>BDX-ANI-NDI</b> and <b>BDX-ANI-xy-NDI</b> where the BDX donor is 2,2,6,6-tetramethylbenzo[1,2-<i>d</i>;4,5-<i>d</i>]bis[1,3]dioxole, the ANI chromophore is 4-(<i>N</i>-piperidinyl)naphthalene-1,8-dicarboximide, the NDI acceptor is naphthalene-1,8:4,5-bis(dicarboximide), and xy is a 2,5-xylyl spacer. The results on these compounds are compared to the analogous derivatives having a <i>p</i>-methoxyaniline (MeOAn) as the donor. BDX<sup>•<b>+</b></sup> has no nitrogen atoms and only a single hydrogen atom coupled to its unpaired electron spin, and therefore has significantly decreased hyperfine interactions compared to MeOAn<sup><b>•+</b></sup>. We use femtosecond transient absorption (fsTA) and nanosecond TA (nsTA) spectroscopies, the latter with an applied static magnetic field, to study the charge transfer dynamics and determine the spin-spin exchange interaction (<i>J</i>) for <b>BDX</b><sup><b>•+</b></sup><b>-ANI-NDI</b><sup><b>•-</b></sup> and <b>BDX</b><sup><b>•+</b></sup><b>-ANI-xy-NDI</b><sup><b>•-</b></sup> at both ambient and cryogenic temperatures. Time-resolved electron paramagnetic resonance (EPR) and pulse-EPR measurements on these spin-correlated radical pairs (SCRPs) were used to probe their spin dynamics. We demonstrate that <b>BDX</b><sup><b>•+</b></sup><b>-ANI-xy-NDI</b><sup><b>•-</b></sup> has an unusually long lifetime of ∼550 μs in glassy butyronitrile (PrCN) at 85 K, which makes it useful for pulse-EPR studies that target quantum information science (QIS) applications. We also show that rotation of the BDX group about the single bond linking it to the neighboring phenyl group has a significant impact on the spin dynamics, and in particular the magnitude of <i>J</i>. By comparing the results on these compounds to the analogous MeOAn series, insights into design principles for creating improved spin-correlated radical pair systems for QIS studies are obtained.</p>\",\"PeriodicalId\":59,\"journal\":{\"name\":\"The Journal of Physical Chemistry A\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":2.7000,\"publicationDate\":\"2024-10-31\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"The Journal of Physical Chemistry A\",\"FirstCategoryId\":\"1\",\"ListUrlMain\":\"https://doi.org/10.1021/acs.jpca.4c05015\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"2024/10/16 0:00:00\",\"PubModel\":\"Epub\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"The Journal of Physical Chemistry A","FirstCategoryId":"1","ListUrlMain":"https://doi.org/10.1021/acs.jpca.4c05015","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2024/10/16 0:00:00","PubModel":"Epub","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Enhancing Photogenerated Radical Pair Properties in Donor-Chromophore-Acceptor Systems for Quantum Information Applications.
We report on new donor-chromophore-acceptor triads BDX-ANI-NDI and BDX-ANI-xy-NDI where the BDX donor is 2,2,6,6-tetramethylbenzo[1,2-d;4,5-d]bis[1,3]dioxole, the ANI chromophore is 4-(N-piperidinyl)naphthalene-1,8-dicarboximide, the NDI acceptor is naphthalene-1,8:4,5-bis(dicarboximide), and xy is a 2,5-xylyl spacer. The results on these compounds are compared to the analogous derivatives having a p-methoxyaniline (MeOAn) as the donor. BDX•+ has no nitrogen atoms and only a single hydrogen atom coupled to its unpaired electron spin, and therefore has significantly decreased hyperfine interactions compared to MeOAn•+. We use femtosecond transient absorption (fsTA) and nanosecond TA (nsTA) spectroscopies, the latter with an applied static magnetic field, to study the charge transfer dynamics and determine the spin-spin exchange interaction (J) for BDX•+-ANI-NDI•- and BDX•+-ANI-xy-NDI•- at both ambient and cryogenic temperatures. Time-resolved electron paramagnetic resonance (EPR) and pulse-EPR measurements on these spin-correlated radical pairs (SCRPs) were used to probe their spin dynamics. We demonstrate that BDX•+-ANI-xy-NDI•- has an unusually long lifetime of ∼550 μs in glassy butyronitrile (PrCN) at 85 K, which makes it useful for pulse-EPR studies that target quantum information science (QIS) applications. We also show that rotation of the BDX group about the single bond linking it to the neighboring phenyl group has a significant impact on the spin dynamics, and in particular the magnitude of J. By comparing the results on these compounds to the analogous MeOAn series, insights into design principles for creating improved spin-correlated radical pair systems for QIS studies are obtained.
期刊介绍:
The Journal of Physical Chemistry A is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, and chemical physicists.