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

Hong, Jiyun; Kelley, Matthew S.; Shelby, Megan L.; Hayes, Dugan K.; Hadt, Ryan G.; Rimmerman, Dolev; Zhang, Xiaoyi; Chen, Lin X.

doi:10.1002/cssc.201800777

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

Journal Article · Thu May 31 00:00:00 EDT 2018 · ChemSusChem

DOI:https://doi.org/10.1002/cssc.201800777· OSTI ID:1465767

Hong, Jiyun ^[1]; Kelley, Matthew S. ^[1]; ^[1]; Hayes, Dugan K. ^[2]; Hadt, Ryan G. ^[2]; Rimmerman, Dolev ^[1]; Zhang, Xiaoyi ^[2]; ^[3]

Northwestern Univ., Evanston, IL (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)
Argonne National Lab. (ANL), Argonne, IL (United States); Northwestern Univ., Evanston, IL (United States)

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.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Light Energy Activated Redox Processes (LEAP); Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1465767

Alternate ID(s):: OSTI ID: 1458835

Journal Information:: ChemSusChem, Journal Name: ChemSusChem Journal Issue: 14 Vol. 11; ISSN 1864-5631

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

References (61)

Resonance Raman spectroscopy of non-planar nickel porphyrins Shelnutt, J. A.; Majumder, S. A.; Sparks, L. D. Journal of Raman Spectroscopy, Vol. 23, Issue 10 https://doi.org/10.1002/jrs.1250231004	journal	October 1992
Phthalocyanines: From outstanding electronic properties to emerging applications Claessens, Christian G.; Hahn, Uwe; Torres, Tomás The Chemical Record, Vol. 8, Issue 2 https://doi.org/10.1002/tcr.20139	journal	January 2008
The ORCA program system: The ORCA program system Neese, Frank Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 1 https://doi.org/10.1002/wcms.81	journal	June 2011
Porphyrins XXVIII. Extended H�ckel calculations on metal phthalocyanines and tetrazaporphins Schaffer, Arnold M.; Gouterman, Martin; Davidson, Ernest R. Theoretica Chimica Acta, Vol. 30, Issue 1 https://doi.org/10.1007/BF00527632	journal	January 1973
Quantitative Cu(I) determination using X-ray absorption edge spectroscopy: Oxidation of the reduced binuclear copper site in type 2 depleted Rhus laccase Hahn, James E.; Co, Man Sung; Spira, Darlene J. Biochemical and Biophysical Research Communications, Vol. 112, Issue 2 https://doi.org/10.1016/0006-291X(83)91524-3	journal	April 1983
Observation of an electric quadrupole transition in the X-ray absorption spectrum of a Cu(II) complex Hahn, James E.; Scott, Robert A.; Hodgson, Keith O. Chemical Physics Letters, Vol. 88, Issue 6 https://doi.org/10.1016/0009-2614(82)85016-1	journal	May 1982
Results obtained with the correlation energy density functionals of becke and Lee, Yang and Parr Miehlich, Burkhard; Savin, Andreas; Stoll, Hermann Chemical Physics Letters, Vol. 157, Issue 3 https://doi.org/10.1016/0009-2614(89)87234-3	journal	May 1989
Metallophthalocyanines as catalysts in electrochemical reactions Zagal, José H. Coordination Chemistry Reviews, Vol. 119 https://doi.org/10.1016/0010-8545(92)80031-L	journal	October 1992
Phthalocyanines. Properties and applications Jayasooriya, UpaliA. Spectrochimica Acta Part A: Molecular Spectroscopy, Vol. 50, Issue 13 https://doi.org/10.1016/0584-8539(94)80190-8	journal	November 1994
Time-dependent density functional theory within the Tamm–Dancoff approximation Hirata, So; Head-Gordon, Martin Chemical Physics Letters, Vol. 314, Issue 3-4 https://doi.org/10.1016/S0009-2614(99)01149-5	journal	December 1999
Metallophthalocyanines Guillaud, G.; Simon, J.; Germain, J. P. Coordination Chemistry Reviews, Vol. 178-180 https://doi.org/10.1016/S0010-8545(98)00177-5	journal	December 1998
Probing transient molecular structures with time-resolved pump/probe XAFS using synchrotron X-ray sources Chen, Lin X. Journal of Electron Spectroscopy and Related Phenomena, Vol. 119, Issue 2-3 https://doi.org/10.1016/S0368-2048(01)00289-4	journal	August 2001
New insight into metalloporphyrin excited state structures and axial ligand binding from X-ray transient absorption spectroscopic studies Shelby, Megan L.; Mara, Michael W.; Chen, Lin X. Coordination Chemistry Reviews, Vol. 277-278 https://doi.org/10.1016/j.ccr.2014.05.025	journal	October 2014
Efficient, approximate and parallel Hartree–Fock and hybrid DFT calculations. A ‘chain-of-spheres’ algorithm for the Hartree–Fock exchange Neese, Frank; Wennmohs, Frank; Hansen, Andreas Chemical Physics, Vol. 356, Issue 1-3 https://doi.org/10.1016/j.chemphys.2008.10.036	journal	February 2009
Comparison of two efficient approximate Hartee–Fock approaches Kossmann, Simone; Neese, Frank Chemical Physics Letters, Vol. 481, Issue 4-6 https://doi.org/10.1016/j.cplett.2009.09.073	journal	October 2009
Design and Synthesis of Porphyrin-Based Optoelectronic Gates Ambroise, Arounaguiry; Wagner, Richard W.; Rao, Polisetti Dharma Chemistry of Materials, Vol. 13, Issue 3 https://doi.org/10.1021/cm000773m	journal	March 2001
Porphyrin vs phthalocyanine metallomacrocycles based one-dimensional "molecular metals". Insights from density functional calculations Rosa, Angela; Baerends, Evert Jan Inorganic Chemistry, Vol. 32, Issue 24 https://doi.org/10.1021/ic00076a037	journal	November 1993
Metal-Macrocycle Interaction in Phthalocyanines: Density Functional Calculations of Ground and Excited States Rosa, A.; Baerends, E. J. Inorganic Chemistry, Vol. 33, Issue 3 https://doi.org/10.1021/ic00081a029	journal	February 1994
Effects of Benzoannulation and α-Octabutoxy Substitution on the Photophysical Behavior of Nickel Phthalocyanines: A Combined Experimental and DFT/TDDFT Study Soldatova, Alexandra V.; Kim, Junhwan; Peng, Xinzhang Inorganic Chemistry, Vol. 46, Issue 6 https://doi.org/10.1021/ic061524o	journal	March 2007
Nonplanar distortion modes for highly substituted porphyrins Medforth, Craig J.; Senge, Mathias O.; Smith, Kevin M. Journal of the American Chemical Society, Vol. 114, Issue 25 https://doi.org/10.1021/ja00051a019	journal	December 1992
Structural and theoretical models of photosynthetic chromophores. Implications for redox, light-absorption properties and vectorial electron flow Barkigia, K. M.; Chantranupong, L.; Smith, K. M. Journal of the American Chemical Society, Vol. 110, Issue 22 https://doi.org/10.1021/ja00230a063	journal	October 1988
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 Kau, Lung Shan; Spira-Solomon, Darlene J.; Penner-Hahn, James E. Journal of the American Chemical Society, Vol. 109, Issue 21 https://doi.org/10.1021/ja00255a032	journal	October 1987
Evidence from picosecond transient absorption and kinetic studies of charge-transfer states in copper(II) porphyrins Kim, Dongho; Holten, Dewey; Gouterman, Martin Journal of the American Chemical Society, Vol. 106, Issue 10 https://doi.org/10.1021/ja00322a012	journal	May 1984
Tracking Electrons and Atoms in a Photoexcited Metalloporphyrin by X-ray Transient Absorption Spectroscopy Chen, Lin X.; Zhang, Xiaoyi; Wasinger, Erik C. Journal of the American Chemical Society, Vol. 129, Issue 31 https://doi.org/10.1021/ja072979v	journal	August 2007
Modulating Heme Redox Potential through Protein-Induced Porphyrin Distortion Olea, Charles; Kuriyan, John; Marletta, Michael A. Journal of the American Chemical Society, Vol. 132, Issue 37 https://doi.org/10.1021/ja106252b	journal	September 2010
Ultrafast Charge Transfer in Nickel Phthalocyanine Probed by Femtosecond Raman-Induced Kerr Effect Spectroscopy Balakrishnan, Gurusamy; Soldatova, Alexandra V.; Reid, Philip J. Journal of the American Chemical Society, Vol. 136, Issue 24 https://doi.org/10.1021/ja503541v	journal	June 2014
Reorganization Energies of Diprotonated and Saddle-Distorted Porphyrins in Photoinduced Electron-Transfer Reduction Controlled by Conformational Distortion Nakanishi, Tatsuaki; Ohkubo, Kei; Kojima, Takahiko Journal of the American Chemical Society, Vol. 131, Issue 2 https://doi.org/10.1021/ja806261q	journal	January 2009
Representation of Nonplanar Structures of Nickel(II) 5,15-Disubstituted Porphyrins in Terms of Displacements along the Lowest-Frequency Normal Coordinates of the Macrocycle Song, Xing-Zhi; Jentzen, Walter; Jia, Song-Ling Journal of the American Chemical Society, Vol. 118, Issue 51 https://doi.org/10.1021/ja961676q	journal	January 1996
A Multiplet Analysis of Fe K-Edge 1s → 3d Pre-Edge Features of Iron Complexes Westre, Tami E.; Kennepohl, Pierre; DeWitt, Jane G. Journal of the American Chemical Society, Vol. 119, Issue 27 https://doi.org/10.1021/ja964352a	journal	July 1997
Picosecond to Microsecond Photodynamics of a Nonplanar Nickel Porphyrin: Solvent Dielectric and Temperature Effects Drain, Charles Michael; Gentemann, Steve; Roberts, James A. Journal of the American Chemical Society, Vol. 120, Issue 15 https://doi.org/10.1021/ja974101h	journal	April 1998
Electron Injection from Copper Diimine Sensitizers into TiO ₂ : Structural Effects and Their Implications for Solar Energy Conversion Devices Mara, Michael W.; Bowman, David N.; Buyukcakir, Onur Journal of the American Chemical Society, Vol. 137, Issue 30 https://doi.org/10.1021/jacs.5b04612	journal	July 2015
Ultrafast Excited State Relaxation of a Metalloporphyrin Revealed by Femtosecond X-ray Absorption Spectroscopy Shelby, Megan L.; Lestrange, Patrick J.; Jackson, Nicholas E. Journal of the American Chemical Society, Vol. 138, Issue 28 https://doi.org/10.1021/jacs.6b02176	journal	July 2016
The Optical Spectra of NiP, NiPz, NiTBP, and NiPc: Electronic Effects of Meso -tetraaza Substitution and Tetrabenzo Annulation Rosa, A.; Ricciardi, G.; Baerends, E. J. The Journal of Physical Chemistry A, Vol. 105, Issue 13 https://doi.org/10.1021/jp003508x	journal	April 2001
Photophysics of Octabutoxy Phthalocyaninato-Ni(II) in Toluene: Ultrafast Experiments and DFT/TDDFT Studies Gunaratne, Tissa C.; Gusev, Alexey V.; Peng, Xinzhan The Journal of Physical Chemistry A, Vol. 109, Issue 10 https://doi.org/10.1021/jp0457444	journal	March 2005
Ultrafast Structural Dynamics of Cu(I)-Bicinchoninic Acid and Their Implications for Solar Energy Applications Fransted, Kelly A.; Jackson, Nicholas E.; Zong, Ruifa The Journal of Physical Chemistry A, Vol. 118, Issue 45 https://doi.org/10.1021/jp504294j	journal	July 2014
Visualizing Interfacial Charge Transfer in Ru-Dye-Sensitized TiO ₂ Nanoparticles Using X-ray Transient Absorption Spectroscopy Zhang, Xiaoyi; Smolentsev, Grigory; Guo, Jianchang The Journal of Physical Chemistry Letters, Vol. 2, Issue 6 https://doi.org/10.1021/jz200122r	journal	February 2011
Photochemical Processes Revealed by X-ray Transient Absorption Spectroscopy Chen, Lin X.; Zhang, Xiaoyi The Journal of Physical Chemistry Letters, Vol. 4, Issue 22 https://doi.org/10.1021/jz401750g	journal	November 2013
Magnetosomes could be protective shields against metal stress in magnetotactic bacteria Muñoz, D.; Marcano, L.; Martín-Rodríguez, R. Scientific Reports, Vol. 10, Issue 1 https://doi.org/10.1038/s41598-020-68183-z	journal	July 2020
Recent advances on ultrafast X-ray spectroscopy in the chemical sciences Chen, L. X.; Zhang, X.; Shelby, M. L. Chem. Sci., Vol. 5, Issue 11 https://doi.org/10.1039/C4SC01333F	journal	January 2014
1,4,8,11,15,18,22,25-Alkylsulfanyl phthalocyanines: effect of macrocycle distortion on spectroscopic and packing properties Zorlu, Yunus; Kumru, Ufuk; İşci, Ümit Chemical Communications, Vol. 51, Issue 30 https://doi.org/10.1039/C5CC01085C	journal	January 2015
Synthesis, structure, ultrafast kinetics, and light-induced dynamics of CuHETPHEN chromophores Kohler, Lars; Hayes, Dugan; Hong, Jiyun Dalton Transactions, Vol. 45, Issue 24 https://doi.org/10.1039/C6DT00324A	journal	January 2016
Phthalocyanines: structure and vibrations Tackley, Daniel R.; Dent, Geoffrey; Ewen Smith, W. Physical Chemistry Chemical Physics, Vol. 3, Issue 8 https://doi.org/10.1039/b007763l	journal	January 2001
Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy Weigend, Florian; Ahlrichs, Reinhart Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305 https://doi.org/10.1039/b508541a	journal	January 2005
Accurate Coulomb-fitting basis sets for H to Rn Weigend, Florian Physical Chemistry Chemical Physics, Vol. 8, Issue 9 https://doi.org/10.1039/b515623h	journal	January 2006
X-ray snapshots for metalloporphyrin axial ligation Chen, Lin X.; Zhang, Xiaoyi; Wasinger, Erik C. Chemical Science, Vol. 1, Issue 5 https://doi.org/10.1039/c0sc00323a	journal	January 2010
182. Conjugated macrocycles. Part XXXII. Absorption spectra of tetrazaporphins and phthalocyanines. Formation of pyridine salts Whalley, Margaret Journal of the Chemical Society (Resumed) https://doi.org/10.1039/jr9610000866	journal	January 1961
Electronic structure and bonding in metal phthalocyanines, Metal=Fe, Co, Ni, Cu, Zn, Mg Liao, Meng-Sheng; Scheiner, Steve The Journal of Chemical Physics, Vol. 114, Issue 22 https://doi.org/10.1063/1.1367374	journal	June 2001
Electronic structure and bonding in metal porphyrins, metal=Fe, Co, Ni, Cu, Zn Liao, Meng-Sheng; Scheiner, Steve The Journal of Chemical Physics, Vol. 117, Issue 1 https://doi.org/10.1063/1.1480872	journal	July 2002
Theoretical analysis of singlet and triplet excited states of nickel porphyrins Patchkovskii, Serguei; Kozlowski, Pawel M.; Zgierski, Marek Z. The Journal of Chemical Physics, Vol. 121, Issue 3 https://doi.org/10.1063/1.1762875	journal	July 2004
An overlap fitted chain of spheres exchange method Izsák, Róbert; Neese, Frank The Journal of Chemical Physics, Vol. 135, Issue 14 https://doi.org/10.1063/1.3646921	journal	October 2011
Density‐functional thermochemistry. III. The role of exact exchange Becke, Axel D. The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652 https://doi.org/10.1063/1.464913	journal	April 1993
Relativistic regular two‐component Hamiltonians Lenthe, E. van; Baerends, E. J.; Snijders, J. G. The Journal of Chemical Physics, Vol. 99, Issue 6 https://doi.org/10.1063/1.466059	journal	September 1993
The ultrafast intramolecular dynamics of phthalocyanine and porphyrin derivatives Zhong, Qinghua; Wang, Zhaohui; Liu, Yunqi The Journal of Chemical Physics, Vol. 105, Issue 13 https://doi.org/10.1063/1.472378	journal	October 1996
Molecular density functional calculations in the regular relativistic approximation: Method, application to coinage metal diatomics, hydrides, fluorides and chlorides, and comparison with first-order relativistic calculations van Wüllen, Christoph The Journal of Chemical Physics, Vol. 109, Issue 2 https://doi.org/10.1063/1.476576	journal	July 1998
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density Lee, Chengteh; Yang, Weitao; Parr, Robert G. Physical Review B, Vol. 37, Issue 2 https://doi.org/10.1103/PhysRevB.37.785	journal	January 1988
IFEFFIT : interactive XAFS analysis and FEFF fitting Newville, Matthew Journal of Synchrotron Radiation, Vol. 8, Issue 2 https://doi.org/10.1107/S0909049500016964	journal	March 2001
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT Ravel, B.; Newville, M. Journal of Synchrotron Radiation, Vol. 12, Issue 4 https://doi.org/10.1107/S0909049505012719	journal	June 2005
Phthalocyanines: Properties and Applications Bommer, Jerry C.; Spikes, John D. Photochemistry and Photobiology, Vol. 53, Issue 3 https://doi.org/10.1111/j.1751-1097.1991.tb03651.x	journal	March 1991
Capturing a Photoexcited Molecular Structure Through Time-Domain X-ray Absorption Fine Structure Chen, L. X. Science, Vol. 292, Issue 5515 https://doi.org/10.1126/science.1057063	journal	April 2001
Probing Transient Molecular Structures in Photochemical Processes Using Laser-Initiated Time-Resolved X-Ray Absorption Spectroscopy Chen, Lin X. Annual Review of Physical Chemistry, Vol. 56, Issue 1 https://doi.org/10.1146/annurev.physchem.56.092503.141310	journal	May 2005
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density Robert, Parr,; Chengteh, Lee,; Weitao, Yang, The University of North Carolina at Chapel Hill University Libraries https://doi.org/10.17615/zrp0-ry04	text	January 1988

Figures / Tables (11)

Similar Records

Investigation of the Photoinduced axial ligation process in the excited state of nickel (II) phthalocyanine

Journal Article · Thu Feb 28 23:00:00 EST 2019 · Journal of Photochemistry and Photobiology. A, Chemistry · OSTI ID:1641748

X-ray snapshots for metalloporphyrin axial ligation

Journal Article · Thu Dec 31 23:00:00 EST 2009 · Chemical Science · OSTI ID:1043153

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Charge transfer
Electronic structure
Photochemistry
Phthalocyanines
X-ray absorption spectroscopy