Yonggang Yang , Feiyao Geng , Zhinan Jiang , Yang Liu , Tiantian Guan , Chaochao Qin , Chunsheng Zhuang , Yufang Liu
{"title":"mCP 和 Br-mCP 的超快动力学：瞬态吸收光谱的启示","authors":"Yonggang Yang , Feiyao Geng , Zhinan Jiang , Yang Liu , Tiantian Guan , Chaochao Qin , Chunsheng Zhuang , Yufang Liu","doi":"10.1016/j.jlumin.2024.120940","DOIUrl":null,"url":null,"abstract":"<div><div>Heavy atom activated organic room-temperature phosphorescence (RTP) has attracted considerable interest due to its high phosphorescence quantum yield and prolonged lifetime. This research provides a detailed analysis of the transient absorption spectroscopy of 1,3-Bis(N-carbazolyl)benzene (mCP) and 9,9'-(5-Bromo-1,3-phenylene)bis(9H-carbazole) (Br-mCP) in toluene solution. In the femtosecond transient absorption (fs-TA) spectroscopy of mCP, the excited state absorption (ESA) signal decreases at 630 nm while the triplet-triplet absorption (TTA) signal increases at 420 nm. Meanwhile, the isosbestic point observed at 455 nm indicates an intersystem crossing (ISC) lifetime of 15.4 ns. Moving on to the nanosecond transient absorption (ns-TA) spectroscopy, the TTA signal reaches its peak at 27.3 ns before decreasing, with the triplet lifetime of mCP measured at 2.8 μs. Br-mCP exhibits a similar dynamic evolution to mCP, but with a quicker ISC process (9.4 ns) and a longer triplet lifetime (3.9 μs). The quicker ISC process in Br-mCP is ascribed to the presence of heavy atom in the molecular structure, leading to an enhanced spin-orbit coupling constant (ξ(S<sub>1</sub>, T<sub>3</sub>)<sub>Br-mCP</sub> = 1.371 cm<sup>−1</sup> > ξ(S<sub>1</sub>, T<sub>4</sub>)<sub>mCP</sub> = 0.060 cm<sup>−1</sup>). The prolonged triplet lifetime of Br-mCP (3.9 μs > 2.8 μs) results from its lower reorganization energy, effectively reducing non-radiative vibrational energy losses within the molecule. This work significantly enhances our understanding of RTP materials incorporating heavy atoms.</div></div>","PeriodicalId":16159,"journal":{"name":"Journal of Luminescence","volume":"277 ","pages":"Article 120940"},"PeriodicalIF":3.3000,"publicationDate":"2024-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Ultrafast dynamics of mCP and Br-mCP: Insights from transient absorption spectroscopy\",\"authors\":\"Yonggang Yang , Feiyao Geng , Zhinan Jiang , Yang Liu , Tiantian Guan , Chaochao Qin , Chunsheng Zhuang , Yufang Liu\",\"doi\":\"10.1016/j.jlumin.2024.120940\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>Heavy atom activated organic room-temperature phosphorescence (RTP) has attracted considerable interest due to its high phosphorescence quantum yield and prolonged lifetime. This research provides a detailed analysis of the transient absorption spectroscopy of 1,3-Bis(N-carbazolyl)benzene (mCP) and 9,9'-(5-Bromo-1,3-phenylene)bis(9H-carbazole) (Br-mCP) in toluene solution. In the femtosecond transient absorption (fs-TA) spectroscopy of mCP, the excited state absorption (ESA) signal decreases at 630 nm while the triplet-triplet absorption (TTA) signal increases at 420 nm. Meanwhile, the isosbestic point observed at 455 nm indicates an intersystem crossing (ISC) lifetime of 15.4 ns. Moving on to the nanosecond transient absorption (ns-TA) spectroscopy, the TTA signal reaches its peak at 27.3 ns before decreasing, with the triplet lifetime of mCP measured at 2.8 μs. Br-mCP exhibits a similar dynamic evolution to mCP, but with a quicker ISC process (9.4 ns) and a longer triplet lifetime (3.9 μs). The quicker ISC process in Br-mCP is ascribed to the presence of heavy atom in the molecular structure, leading to an enhanced spin-orbit coupling constant (ξ(S<sub>1</sub>, T<sub>3</sub>)<sub>Br-mCP</sub> = 1.371 cm<sup>−1</sup> > ξ(S<sub>1</sub>, T<sub>4</sub>)<sub>mCP</sub> = 0.060 cm<sup>−1</sup>). The prolonged triplet lifetime of Br-mCP (3.9 μs > 2.8 μs) results from its lower reorganization energy, effectively reducing non-radiative vibrational energy losses within the molecule. This work significantly enhances our understanding of RTP materials incorporating heavy atoms.</div></div>\",\"PeriodicalId\":16159,\"journal\":{\"name\":\"Journal of Luminescence\",\"volume\":\"277 \",\"pages\":\"Article 120940\"},\"PeriodicalIF\":3.3000,\"publicationDate\":\"2024-10-12\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Luminescence\",\"FirstCategoryId\":\"101\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0022231324005040\",\"RegionNum\":3,\"RegionCategory\":\"物理与天体物理\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"OPTICS\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Luminescence","FirstCategoryId":"101","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0022231324005040","RegionNum":3,"RegionCategory":"物理与天体物理","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"OPTICS","Score":null,"Total":0}
Ultrafast dynamics of mCP and Br-mCP: Insights from transient absorption spectroscopy
Heavy atom activated organic room-temperature phosphorescence (RTP) has attracted considerable interest due to its high phosphorescence quantum yield and prolonged lifetime. This research provides a detailed analysis of the transient absorption spectroscopy of 1,3-Bis(N-carbazolyl)benzene (mCP) and 9,9'-(5-Bromo-1,3-phenylene)bis(9H-carbazole) (Br-mCP) in toluene solution. In the femtosecond transient absorption (fs-TA) spectroscopy of mCP, the excited state absorption (ESA) signal decreases at 630 nm while the triplet-triplet absorption (TTA) signal increases at 420 nm. Meanwhile, the isosbestic point observed at 455 nm indicates an intersystem crossing (ISC) lifetime of 15.4 ns. Moving on to the nanosecond transient absorption (ns-TA) spectroscopy, the TTA signal reaches its peak at 27.3 ns before decreasing, with the triplet lifetime of mCP measured at 2.8 μs. Br-mCP exhibits a similar dynamic evolution to mCP, but with a quicker ISC process (9.4 ns) and a longer triplet lifetime (3.9 μs). The quicker ISC process in Br-mCP is ascribed to the presence of heavy atom in the molecular structure, leading to an enhanced spin-orbit coupling constant (ξ(S1, T3)Br-mCP = 1.371 cm−1 > ξ(S1, T4)mCP = 0.060 cm−1). The prolonged triplet lifetime of Br-mCP (3.9 μs > 2.8 μs) results from its lower reorganization energy, effectively reducing non-radiative vibrational energy losses within the molecule. This work significantly enhances our understanding of RTP materials incorporating heavy atoms.
期刊介绍：
The purpose of the Journal of Luminescence is to provide a means of communication between scientists in different disciplines who share a common interest in the electronic excited states of molecular, ionic and covalent systems, whether crystalline, amorphous, or liquid.
We invite original papers and reviews on such subjects as: exciton and polariton dynamics, dynamics of localized excited states, energy and charge transport in ordered and disordered systems, radiative and non-radiative recombination, relaxation processes, vibronic interactions in electronic excited states, photochemistry in condensed systems, excited state resonance, double resonance, spin dynamics, selective excitation spectroscopy, hole burning, coherent processes in excited states, (e.g. coherent optical transients, photon echoes, transient gratings), multiphoton processes, optical bistability, photochromism, and new techniques for the study of excited states. This list is not intended to be exhaustive. Papers in the traditional areas of optical spectroscopy (absorption, MCD, luminescence, Raman scattering) are welcome. Papers on applications (phosphors, scintillators, electro- and cathodo-luminescence, radiography, bioimaging, solar energy, energy conversion, etc.) are also welcome if they present results of scientific, rather than only technological interest. However, papers containing purely theoretical results, not related to phenomena in the excited states, as well as papers using luminescence spectroscopy to perform routine analytical chemistry or biochemistry procedures, are outside the scope of the journal. Some exceptions will be possible at the discretion of the editors.
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