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Nonadiabatic Charge Transfer within Photoexcited Nickel Porphyrins

Naumova, Maria A. ; Paveliuc, Gheorghe ; Biednov, Mykola ; Kubicek, Katharina ; Kalinko, Aleksandr ; Meng, Jie LU ; Liang, Mingli LU ; Rahaman, Ahibur LU ; Abdellah, Mohamed and Checchia, Stefano LU orcid , et al. (2024) In Journal of Physical Chemistry Letters 15(13). p.3627-3638
Abstract

Metalloporphyrins with open d-shell ions can drive biochemical energy cycles. However, their utilization in photoconversion is hampered by rapid deactivation. Mapping the relaxation pathways is essential for elaborating strategies that can favorably alter the charge dynamics through chemical design and photoexcitation conditions. Here, we combine transient optical absorption spectroscopy and transient X-ray emission spectroscopy with femtosecond resolution to probe directly the coupled electronic and spin dynamics within a photoexcited nickel porphyrin in solution. Measurements and calculations reveal that a state with charge-transfer character mediates the formation of the thermalized excited state, thereby advancing the description of... (More)

Metalloporphyrins with open d-shell ions can drive biochemical energy cycles. However, their utilization in photoconversion is hampered by rapid deactivation. Mapping the relaxation pathways is essential for elaborating strategies that can favorably alter the charge dynamics through chemical design and photoexcitation conditions. Here, we combine transient optical absorption spectroscopy and transient X-ray emission spectroscopy with femtosecond resolution to probe directly the coupled electronic and spin dynamics within a photoexcited nickel porphyrin in solution. Measurements and calculations reveal that a state with charge-transfer character mediates the formation of the thermalized excited state, thereby advancing the description of the photocycle for this important representative molecule. More generally, establishing that intramolecular charge-transfer steps play a role in the photoinduced dynamics of metalloporphyrins with open d-shell sets a conceptual ground for their development as building blocks capable of boosting nonadiabatic photoconversion in functional architectures through “hot” charge transfer down to the attosecond time scale.

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organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Journal of Physical Chemistry Letters
volume
15
issue
13
pages
12 pages
publisher
The American Chemical Society (ACS)
external identifiers
  • pmid:38530393
  • scopus:85189026458
ISSN
1948-7185
DOI
10.1021/acs.jpclett.4c00375
language
English
LU publication?
yes
id
7083623d-50f7-43d7-adc7-05437bc74811
date added to LUP
2024-04-11 14:44:53
date last changed
2024-04-25 17:41:36
@article{7083623d-50f7-43d7-adc7-05437bc74811,
  abstract     = {{<p>Metalloporphyrins with open d-shell ions can drive biochemical energy cycles. However, their utilization in photoconversion is hampered by rapid deactivation. Mapping the relaxation pathways is essential for elaborating strategies that can favorably alter the charge dynamics through chemical design and photoexcitation conditions. Here, we combine transient optical absorption spectroscopy and transient X-ray emission spectroscopy with femtosecond resolution to probe directly the coupled electronic and spin dynamics within a photoexcited nickel porphyrin in solution. Measurements and calculations reveal that a state with charge-transfer character mediates the formation of the thermalized excited state, thereby advancing the description of the photocycle for this important representative molecule. More generally, establishing that intramolecular charge-transfer steps play a role in the photoinduced dynamics of metalloporphyrins with open d-shell sets a conceptual ground for their development as building blocks capable of boosting nonadiabatic photoconversion in functional architectures through “hot” charge transfer down to the attosecond time scale.</p>}},
  author       = {{Naumova, Maria A. and Paveliuc, Gheorghe and Biednov, Mykola and Kubicek, Katharina and Kalinko, Aleksandr and Meng, Jie and Liang, Mingli and Rahaman, Ahibur and Abdellah, Mohamed and Checchia, Stefano and Alves Lima, Frederico and Zalden, Peter and Gawelda, Wojciech and Bressler, Christian and Geng, Huifang and Lin, Weihua and Liu, Yan and Zhao, Qian and Pan, Qinying and Akter, Marufa and Kong, Qingyu and Retegan, Marius and Gosztola, David J. and Pápai, Mátyás and Khakhulin, Dmitry and Lawson Daku, Max and Zheng, Kaibo and Canton, Sophie E.}},
  issn         = {{1948-7185}},
  language     = {{eng}},
  number       = {{13}},
  pages        = {{3627--3638}},
  publisher    = {{The American Chemical Society (ACS)}},
  series       = {{Journal of Physical Chemistry Letters}},
  title        = {{Nonadiabatic Charge Transfer within Photoexcited Nickel Porphyrins}},
  url          = {{http://dx.doi.org/10.1021/acs.jpclett.4c00375}},
  doi          = {{10.1021/acs.jpclett.4c00375}},
  volume       = {{15}},
  year         = {{2024}},
}