Ultrafast electronic and vibrational dynamics in brominated aluminum corroles: Energy relaxation and triplet formation
We combined femtosecond (fs) VIS pump–IR probe spectroscopy with fs VIS pump–supercontinuum probe spectroscopy to characterize the photoreaction of the hexacoordinated Al(tpfc-Br8)(py)2 in a comprehensive way. Upon fs excitation at ∼400 nm in the Soret band, the excitation energy relaxes with a time...
| Main Authors: | , , , , , |
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| Format: | Article |
| Language: | English |
| Published: |
AIP Publishing LLC and ACA
2016-07-01
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| Series: | Structural Dynamics |
| Online Access: | http://dx.doi.org/10.1063/1.4949363 |
| _version_ | 1818910110548754432 |
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| author | T. Stensitzki Y. Yang A. Berg A. Mahammed Z. Gross K. Heyne |
| author_facet | T. Stensitzki Y. Yang A. Berg A. Mahammed Z. Gross K. Heyne |
| author_sort | T. Stensitzki |
| collection | DOAJ |
| description | We combined femtosecond (fs) VIS pump–IR probe spectroscopy with fs VIS pump–supercontinuum probe spectroscopy to characterize the photoreaction of the hexacoordinated Al(tpfc-Br8)(py)2 in a comprehensive way. Upon fs excitation at ∼400 nm in the Soret band, the excitation energy relaxes with a time constant of (250 ± 80) fs to the S2 and S1 electronic excited states. This is evident from the rise time of the stimulated emission signal in the visible spectral range. On the same time scale, narrowing of broad infrared signals in the C=C stretching region around 1500 cm−1 is observed. Energy redistribution processes are visible in the vibrational and electronic dynamics with time constants between ∼2 ps and ∼20 ps. Triplet formation is detected with a time constant of (95 ± 3) ps. This is tracked by the complete loss of stimulated emission. Electronic transition of the emerging triplet absorption band overlaps considerably with the singlet excited state absorption. In contrast, two well separated vibrational marker bands for triplet formation were identified at 1477 cm−1 and at 1508 cm−1. These marker bands allow a precise identification of triplet dynamics in corrole systems. |
| first_indexed | 2024-12-19T22:37:36Z |
| format | Article |
| id | doaj.art-47fac5a9654343409ca61063260505d9 |
| institution | Directory Open Access Journal |
| issn | 2329-7778 |
| language | English |
| last_indexed | 2024-12-19T22:37:36Z |
| publishDate | 2016-07-01 |
| publisher | AIP Publishing LLC and ACA |
| record_format | Article |
| series | Structural Dynamics |
| spelling | doaj.art-47fac5a9654343409ca61063260505d92022-12-21T20:03:09ZengAIP Publishing LLC and ACAStructural Dynamics2329-77782016-07-0134043210043210-910.1063/1.4949363023693SDYUltrafast electronic and vibrational dynamics in brominated aluminum corroles: Energy relaxation and triplet formationT. Stensitzki0Y. Yang1A. Berg2A. Mahammed3Z. Gross4K. Heyne5 Institute of Experimental Physics, Free University Berlin, Arnimallee 14, 14195 Berlin, Germany Institute of Experimental Physics, Free University Berlin, Arnimallee 14, 14195 Berlin, Germany Institute of Chemistry, The Hebrew University of Jerusalem, Jerusalem 91904, Israel Technion-Israel Institute of Technology, Schulich Faculty of Chemistry, Haifa 32000, Israel Technion-Israel Institute of Technology, Schulich Faculty of Chemistry, Haifa 32000, Israel Institute of Experimental Physics, Free University Berlin, Arnimallee 14, 14195 Berlin, GermanyWe combined femtosecond (fs) VIS pump–IR probe spectroscopy with fs VIS pump–supercontinuum probe spectroscopy to characterize the photoreaction of the hexacoordinated Al(tpfc-Br8)(py)2 in a comprehensive way. Upon fs excitation at ∼400 nm in the Soret band, the excitation energy relaxes with a time constant of (250 ± 80) fs to the S2 and S1 electronic excited states. This is evident from the rise time of the stimulated emission signal in the visible spectral range. On the same time scale, narrowing of broad infrared signals in the C=C stretching region around 1500 cm−1 is observed. Energy redistribution processes are visible in the vibrational and electronic dynamics with time constants between ∼2 ps and ∼20 ps. Triplet formation is detected with a time constant of (95 ± 3) ps. This is tracked by the complete loss of stimulated emission. Electronic transition of the emerging triplet absorption band overlaps considerably with the singlet excited state absorption. In contrast, two well separated vibrational marker bands for triplet formation were identified at 1477 cm−1 and at 1508 cm−1. These marker bands allow a precise identification of triplet dynamics in corrole systems.http://dx.doi.org/10.1063/1.4949363 |
| spellingShingle | T. Stensitzki Y. Yang A. Berg A. Mahammed Z. Gross K. Heyne Ultrafast electronic and vibrational dynamics in brominated aluminum corroles: Energy relaxation and triplet formation Structural Dynamics |
| title | Ultrafast electronic and vibrational dynamics in brominated aluminum corroles: Energy relaxation and triplet formation |
| title_full | Ultrafast electronic and vibrational dynamics in brominated aluminum corroles: Energy relaxation and triplet formation |
| title_fullStr | Ultrafast electronic and vibrational dynamics in brominated aluminum corroles: Energy relaxation and triplet formation |
| title_full_unstemmed | Ultrafast electronic and vibrational dynamics in brominated aluminum corroles: Energy relaxation and triplet formation |
| title_short | Ultrafast electronic and vibrational dynamics in brominated aluminum corroles: Energy relaxation and triplet formation |
| title_sort | ultrafast electronic and vibrational dynamics in brominated aluminum corroles energy relaxation and triplet formation |
| url | http://dx.doi.org/10.1063/1.4949363 |
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