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

The nature of the photoexcited state of octabutoxy nickel(II) phthalocyanine (NiPcOBu8) with a 500ps 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 NiPcOBu 8 were measured. Based on the results, we identified that the excited state exhibits spectral features that are characteristic of a Ni-1,Ni-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.
Authors:
 [1] ;  [1] ; ORCiD logo [1] ;  [2] ;  [2] ;  [1] ;  [2] ; ORCiD logo [3]
  1. Northwestern Univ., Evanston, IL (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States); Northwestern Univ., Evanston, IL (United States)
Publication Date:
Grant/Contract Number:
AC02-06CH11357
Type:
Accepted Manuscript
Journal Name:
ChemSusChem
Additional Journal Information:
Journal Volume: 11; Journal Issue: 14; Journal ID: ISSN 1864-5631
Publisher:
ChemPubSoc Europe
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Charge transfer; Electronic structure; Photochemistry; Phthalocyanines; X-ray absorption spectroscopy
OSTI Identifier:
1465767
Alternate Identifier(s):
OSTI ID: 1458835

Hong, Jiyun, Kelley, Matthew S., Shelby, Megan L., Hayes, Dugan K., Hadt, Ryan G., Rimmerman, Dolev, Zhang, Xiaoyi, and Chen, Lin X.. The Nature of the Long-Lived Excited State in a NiII Phthalocyanine Complex Investigated by X-Ray Transient Absorption Spectroscopy. United States: N. p., Web. doi:10.1002/cssc.201800777.
Hong, Jiyun, Kelley, Matthew S., Shelby, Megan L., Hayes, Dugan K., Hadt, Ryan G., Rimmerman, Dolev, Zhang, Xiaoyi, & Chen, Lin X.. The Nature of the Long-Lived Excited State in a NiII Phthalocyanine Complex Investigated by X-Ray Transient Absorption Spectroscopy. United States. doi:10.1002/cssc.201800777.
Hong, Jiyun, Kelley, Matthew S., Shelby, Megan L., Hayes, Dugan K., Hadt, Ryan G., Rimmerman, Dolev, Zhang, Xiaoyi, and Chen, Lin X.. 2018. "The Nature of the Long-Lived Excited State in a NiII Phthalocyanine Complex Investigated by X-Ray Transient Absorption Spectroscopy". United States. doi:10.1002/cssc.201800777.
@article{osti_1465767,
title = {The Nature of the Long-Lived Excited State in a NiII Phthalocyanine Complex Investigated by X-Ray Transient Absorption Spectroscopy},
author = {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.},
abstractNote = {The nature of the photoexcited state of octabutoxy nickel(II) phthalocyanine (NiPcOBu8) with a 500ps 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,Ni-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.},
doi = {10.1002/cssc.201800777},
journal = {ChemSusChem},
number = 14,
volume = 11,
place = {United States},
year = {2018},
month = {5}
}

Works referenced in this record:

Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy
journal, January 2005
  • Weigend, Florian; Ahlrichs, Reinhart
  • Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305
  • DOI: 10.1039/b508541a

Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993
  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
  • DOI: 10.1063/1.464913