skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

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

Abstract

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:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Light Energy Activated Redox Processes (LEAP); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1465767
Alternate Identifier(s):
OSTI ID: 1458835
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
ChemSusChem
Additional Journal Information:
Journal Volume: 11; Journal Issue: 14; Journal ID: ISSN 1864-5631
Publisher:
ChemPubSoc Europe
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

Citation Formats

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., 2018. 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. Thu . "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. https://www.osti.gov/servlets/purl/1465767.
@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}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 2 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Ultrafast Structural Dynamics of Cu(I)-Bicinchoninic Acid and Their Implications for Solar Energy Applications
journal, July 2014

  • Fransted, Kelly A.; Jackson, Nicholas E.; Zong, Ruifa
  • The Journal of Physical Chemistry A, Vol. 118, Issue 45
  • DOI: 10.1021/jp504294j

ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
journal, June 2005


Reorganization Energies of Diprotonated and Saddle-Distorted Porphyrins in Photoinduced Electron-Transfer Reduction Controlled by Conformational Distortion
journal, January 2009

  • Nakanishi, Tatsuaki; Ohkubo, Kei; Kojima, Takahiko
  • Journal of the American Chemical Society, Vol. 131, Issue 2
  • DOI: 10.1021/ja806261q

Observation of an electric quadrupole transition in the X-ray absorption spectrum of a Cu(II) complex
journal, May 1982


Phthalocyanines: Properties and Applications
journal, March 1991


The ORCA program system: The ORCA program system
journal, June 2011

  • Neese, Frank
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 1
  • DOI: 10.1002/wcms.81

Phthalocyanines: structure and vibrations
journal, January 2001

  • Tackley, Daniel R.; Dent, Geoffrey; Ewen Smith, W.
  • Physical Chemistry Chemical Physics, Vol. 3, Issue 8
  • DOI: 10.1039/b007763l

Representation of Nonplanar Structures of Nickel(II) 5,15-Disubstituted Porphyrins in Terms of Displacements along the Lowest-Frequency Normal Coordinates of the Macrocycle
journal, January 1996

  • Song, Xing-Zhi; Jentzen, Walter; Jia, Song-Ling
  • Journal of the American Chemical Society, Vol. 118, Issue 51
  • DOI: 10.1021/ja961676q

Design and Synthesis of Porphyrin-Based Optoelectronic Gates
journal, March 2001

  • Ambroise, Arounaguiry; Wagner, Richard W.; Rao, Polisetti Dharma
  • Chemistry of Materials, Vol. 13, Issue 3
  • DOI: 10.1021/cm000773m

Electron Injection from Copper Diimine Sensitizers into TiO 2 : Structural Effects and Their Implications for Solar Energy Conversion Devices
journal, July 2015

  • Mara, Michael W.; Bowman, David N.; Buyukcakir, Onur
  • Journal of the American Chemical Society, Vol. 137, Issue 30
  • DOI: 10.1021/jacs.5b04612

Effects of Benzoannulation and α-Octabutoxy Substitution on the Photophysical Behavior of Nickel Phthalocyanines:  A Combined Experimental and DFT/TDDFT Study
journal, March 2007

  • Soldatova, Alexandra V.; Kim, Junhwan; Peng, Xinzhang
  • Inorganic Chemistry, Vol. 46, Issue 6
  • DOI: 10.1021/ic061524o

Results obtained with the correlation energy density functionals of becke and Lee, Yang and Parr
journal, May 1989


Picosecond to Microsecond Photodynamics of a Nonplanar Nickel Porphyrin:  Solvent Dielectric and Temperature Effects
journal, April 1998

  • Drain, Charles Michael; Gentemann, Steve; Roberts, James A.
  • Journal of the American Chemical Society, Vol. 120, Issue 15
  • DOI: 10.1021/ja974101h

X-ray snapshots for metalloporphyrin axial ligation
journal, January 2010

  • Chen, Lin X.; Zhang, Xiaoyi; Wasinger, Erik C.
  • Chemical Science, Vol. 1, Issue 5
  • DOI: 10.1039/c0sc00323a

Ultrafast Excited State Relaxation of a Metalloporphyrin Revealed by Femtosecond X-ray Absorption Spectroscopy
journal, July 2016

  • Shelby, Megan L.; Lestrange, Patrick J.; Jackson, Nicholas E.
  • Journal of the American Chemical Society, Vol. 138, Issue 28
  • DOI: 10.1021/jacs.6b02176

Structural and theoretical models of photosynthetic chromophores. Implications for redox, light-absorption properties and vectorial electron flow
journal, October 1988

  • Barkigia, K. M.; Chantranupong, L.; Smith, K. M.
  • Journal of the American Chemical Society, Vol. 110, Issue 22
  • DOI: 10.1021/ja00230a063

Synthesis, structure, ultrafast kinetics, and light-induced dynamics of CuHETPHEN chromophores
journal, January 2016

  • Kohler, Lars; Hayes, Dugan; Hong, Jiyun
  • Dalton Transactions, Vol. 45, Issue 24
  • DOI: 10.1039/C6DT00324A

Quantitative Cu(I) determination using X-ray absorption edge spectroscopy: Oxidation of the reduced binuclear copper site in type 2 depleted Rhus laccase
journal, April 1983

  • Hahn, James E.; Co, Man Sung; Spira, Darlene J.
  • Biochemical and Biophysical Research Communications, Vol. 112, Issue 2
  • DOI: 10.1016/0006-291X(83)91524-3

Recent advances on ultrafast X-ray spectroscopy in the chemical sciences
journal, January 2014

  • Chen, L. X.; Zhang, X.; Shelby, M. L.
  • Chem. Sci., Vol. 5, Issue 11
  • DOI: 10.1039/C4SC01333F

1,4,8,11,15,18,22,25-Alkylsulfanyl phthalocyanines: effect of macrocycle distortion on spectroscopic and packing properties
journal, January 2015

  • Zorlu, Yunus; Kumru, Ufuk; İşci, Ümit
  • Chemical Communications, Vol. 51, Issue 30
  • DOI: 10.1039/C5CC01085C

Ultrafast Charge Transfer in Nickel Phthalocyanine Probed by Femtosecond Raman-Induced Kerr Effect Spectroscopy
journal, June 2014

  • Balakrishnan, Gurusamy; Soldatova, Alexandra V.; Reid, Philip J.
  • Journal of the American Chemical Society, Vol. 136, Issue 24
  • DOI: 10.1021/ja503541v

Accurate Coulomb-fitting basis sets for H to Rn
journal, January 2006

  • Weigend, Florian
  • Physical Chemistry Chemical Physics, Vol. 8, Issue 9
  • DOI: 10.1039/b515623h

Theoretical analysis of singlet and triplet excited states of nickel porphyrins
journal, July 2004

  • Patchkovskii, Serguei; Kozlowski, Pawel M.; Zgierski, Marek Z.
  • The Journal of Chemical Physics, Vol. 121, Issue 3
  • DOI: 10.1063/1.1762875

An overlap fitted chain of spheres exchange method
journal, October 2011

  • Izsák, Róbert; Neese, Frank
  • The Journal of Chemical Physics, Vol. 135, Issue 14
  • DOI: 10.1063/1.3646921

Porphyrin vs phthalocyanine metallomacrocycles based one-dimensional "molecular metals". Insights from density functional calculations
journal, November 1993

  • Rosa, Angela; Baerends, Evert Jan
  • Inorganic Chemistry, Vol. 32, Issue 24
  • DOI: 10.1021/ic00076a037

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

Comparison of two efficient approximate Hartee–Fock approaches
journal, October 2009


New insight into metalloporphyrin excited state structures and axial ligand binding from X-ray transient absorption spectroscopic studies
journal, October 2014

  • Shelby, Megan L.; Mara, Michael W.; Chen, Lin X.
  • Coordination Chemistry Reviews, Vol. 277-278
  • DOI: 10.1016/j.ccr.2014.05.025

Electronic structure and bonding in metal porphyrins, metal=Fe, Co, Ni, Cu, Zn
journal, July 2002

  • Liao, Meng-Sheng; Scheiner, Steve
  • The Journal of Chemical Physics, Vol. 117, Issue 1
  • DOI: 10.1063/1.1480872

Porphyrins XXVIII. Extended H�ckel calculations on metal phthalocyanines and tetrazaporphins
journal, January 1973

  • Schaffer, Arnold M.; Gouterman, Martin; Davidson, Ernest R.
  • Theoretica Chimica Acta, Vol. 30, Issue 1
  • DOI: 10.1007/BF00527632

X-ray absorption edge determination of the oxidation state and coordination number of copper. Application to the type 3 site in Rhus vernicifera laccase and its reaction with oxygen
journal, October 1987

  • Kau, Lung Shan; Spira-Solomon, Darlene J.; Penner-Hahn, James E.
  • Journal of the American Chemical Society, Vol. 109, Issue 21
  • DOI: 10.1021/ja00255a032

Metal-Macrocycle Interaction in Phthalocyanines: Density Functional Calculations of Ground and Excited States
journal, February 1994


Evidence from picosecond transient absorption and kinetic studies of charge-transfer states in copper(II) porphyrins
journal, May 1984

  • Kim, Dongho; Holten, Dewey; Gouterman, Martin
  • Journal of the American Chemical Society, Vol. 106, Issue 10
  • DOI: 10.1021/ja00322a012

Probing transient molecular structures with time-resolved pump/probe XAFS using synchrotron X-ray sources
journal, August 2001


Time-dependent density functional theory within the Tamm–Dancoff approximation
journal, December 1999


A Multiplet Analysis of Fe K-Edge 1s → 3d Pre-Edge Features of Iron Complexes
journal, July 1997

  • Westre, Tami E.; Kennepohl, Pierre; DeWitt, Jane G.
  • Journal of the American Chemical Society, Vol. 119, Issue 27
  • DOI: 10.1021/ja964352a

Resonance Raman spectroscopy of non-planar nickel porphyrins
journal, October 1992

  • Shelnutt, J. A.; Majumder, S. A.; Sparks, L. D.
  • Journal of Raman Spectroscopy, Vol. 23, Issue 10
  • DOI: 10.1002/jrs.1250231004

Nonplanar distortion modes for highly substituted porphyrins
journal, December 1992

  • Medforth, Craig J.; Senge, Mathias O.; Smith, Kevin M.
  • Journal of the American Chemical Society, Vol. 114, Issue 25
  • DOI: 10.1021/ja00051a019

Tracking Electrons and Atoms in a Photoexcited Metalloporphyrin by X-ray Transient Absorption Spectroscopy
journal, August 2007

  • Chen, Lin X.; Zhang, Xiaoyi; Wasinger, Erik C.
  • Journal of the American Chemical Society, Vol. 129, Issue 31
  • DOI: 10.1021/ja072979v

Metallophthalocyanines as catalysts in electrochemical reactions
journal, October 1992


The Optical Spectra of NiP, NiPz, NiTBP, and NiPc:  Electronic Effects of Meso -tetraaza Substitution and Tetrabenzo Annulation
journal, April 2001

  • Rosa, A.; Ricciardi, G.; Baerends, E. J.
  • The Journal of Physical Chemistry A, Vol. 105, Issue 13
  • DOI: 10.1021/jp003508x

Metallophthalocyanines
journal, December 1998


Photochemical Processes Revealed by X-ray Transient Absorption Spectroscopy
journal, November 2013

  • Chen, Lin X.; Zhang, Xiaoyi
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 22
  • DOI: 10.1021/jz401750g

Electronic structure and bonding in metal phthalocyanines, Metal=Fe, Co, Ni, Cu, Zn, Mg
journal, June 2001

  • Liao, Meng-Sheng; Scheiner, Steve
  • The Journal of Chemical Physics, Vol. 114, Issue 22
  • DOI: 10.1063/1.1367374

Relativistic regular two‐component Hamiltonians
journal, September 1993

  • Lenthe, E. van; Baerends, E. J.; Snijders, J. G.
  • The Journal of Chemical Physics, Vol. 99, Issue 6
  • DOI: 10.1063/1.466059

Visualizing Interfacial Charge Transfer in Ru-Dye-Sensitized TiO 2 Nanoparticles Using X-ray Transient Absorption Spectroscopy
journal, February 2011

  • Zhang, Xiaoyi; Smolentsev, Grigory; Guo, Jianchang
  • The Journal of Physical Chemistry Letters, Vol. 2, Issue 6
  • DOI: 10.1021/jz200122r

The ultrafast intramolecular dynamics of phthalocyanine and porphyrin derivatives
journal, October 1996

  • Zhong, Qinghua; Wang, Zhaohui; Liu, Yunqi
  • The Journal of Chemical Physics, Vol. 105, Issue 13
  • DOI: 10.1063/1.472378

Phthalocyanines: From outstanding electronic properties to emerging applications
journal, January 2008

  • Claessens, Christian G.; Hahn, Uwe; Torres, Tomás
  • The Chemical Record, Vol. 8, Issue 2
  • DOI: 10.1002/tcr.20139

Modulating Heme Redox Potential through Protein-Induced Porphyrin Distortion
journal, September 2010

  • Olea, Charles; Kuriyan, John; Marletta, Michael A.
  • Journal of the American Chemical Society, Vol. 132, Issue 37
  • DOI: 10.1021/ja106252b

IFEFFIT  : interactive XAFS analysis and FEFF fitting
journal, March 2001


Photophysics of Octabutoxy Phthalocyaninato-Ni(II) in Toluene:  Ultrafast Experiments and DFT/TDDFT Studies
journal, March 2005

  • Gunaratne, Tissa C.; Gusev, Alexey V.; Peng, Xinzhan
  • The Journal of Physical Chemistry A, Vol. 109, Issue 10
  • DOI: 10.1021/jp0457444