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The Nature of the Long-Lived Excited State in a Ni^(II) Phthalocyanine Complex Investigated by X-Ray Transient Absorption Spectroscopy

Hong, Jiyun and Kelley, Matthew S. and Shelby, Megan L. and Hayes, Dugan K. and Hadt, Ryan G. and Rimmerman, Dolev and Zhang, Xiaoyi and Chen, Lin X. (2018) The Nature of the Long-Lived Excited State in a Ni^(II) Phthalocyanine Complex Investigated by X-Ray Transient Absorption Spectroscopy. ChemSusChem, 11 (14). pp. 2421-2428. ISSN 1864-5631. https://resolver.caltech.edu/CaltechAUTHORS:20200410-115330197

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Abstract

The nature of the photoexcited state of octabutoxy nickel(II) phthalocyanine (NiPcOBu₈) with a 500 ps lifetime was investigated by X‐ray transient absorption (XTA) spectroscopy. Previous optical, vibrational, and computational studies have suggested that this photoexcited state has a ligand‐to‐metal charge transfer (LMCT) nature. By using XTA, which provides unambiguous information on the local electronic and nuclear configuration around the Ni center, the nature of the excited state of NiPcOBu₈ was reassessed. Using X‐ray probe pulses from a synchrotron source, the ground‐ and excited‐state X‐ray absorption spectra of NiPcOBu8 were measured. Based on the results, we identified that the excited state exhibits spectral features that are characteristic of a Ni^(1, 3)(3d_(z²), 3d_(x²-y²)) state rather than a LMCT state with a transiently reduced Ni center. This state resembles the (d,d) state of nickel(II) tetramesitylphorphyrin. The XTA features are rationalized based on the inherent cavity sizes of the macrocycles. These results may provide useful guidance for the design of photocatalysts in the future.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1002/cssc.201800777DOIArticle
ORCID:
AuthorORCID
Shelby, Megan L.0000-0001-6984-957X
Hadt, Ryan G.0000-0001-6026-1358
Zhang, Xiaoyi0000-0001-9732-1449
Chen, Lin X.0000-0002-8450-6687
Additional Information:© 2018 Wiley‐VCH. Manuscript received: April 10, 2018. Revised manuscript received: May 24, 2018. Accepted manuscript online:May 31, 2018. Version of record online: July 4, 2018. This work was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, through Argonne National Laboratory (ANL) under Contract No. DE‐AC02‐06CH11357. J. H. acknowledges the support from Argonne‐Northwestern Solar Energy Research (ANSER) Center, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE‐SC0001059. D.H. acknowledges support from the Joseph J. Katz Fellowship from ANL, and R.G.H. acknowledges support from the Enrico Fermi Fellowship from ANL. Use of the Advanced Photon Source (APS) at ANL is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE‐AC02‐06CH11357. The authors declare no conflict of interest.
Funders:
Funding AgencyGrant Number
Department of Energy (DOE)DE‐AC02‐06CH11357
Department of Energy (DOE)DE‐SC0001059
Argonne National LaboratoryUNSPECIFIED
Subject Keywords:charge transfer; electronic structure ;photochemistry; phthalocyanines; x-ray absorption spectroscopy
Issue or Number:14
Record Number:CaltechAUTHORS:20200410-115330197
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20200410-115330197
Official Citation:J. Hong, M. S. Kelley, M. L. Shelby, D. K. Hayes, R. G. Hadt, D. Rimmerman, X. Zhang, L. X. Chen, ChemSusChem 2018, 11, 2421.
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:102486
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:10 Apr 2020 19:40
Last Modified:10 Apr 2020 19:40

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