Identification of the dominant photochemical pathways and mechanistic insights to the ultrafast ligand exchange of Fe(CO)5 to Fe(CO)4EtOH

Kunnus, K.; Josefsson, I.; Rajkovic, I.; Schreck, S.; Quevedo, W.; Beye, M.; Weniger, C.; Grübel, S.; Scholz, M.; Nordlund, D.; Zhang, W.; Hartsock, R. W.; Gaffney, K. J.; Schlotter, W. F.; Turner, J. J.; Kennedy, B.; Hennies, F.; de Groot, F. M.  F.; Techert, S.; Odelius, M.; Wernet, Ph.; Föhlisch, A.

doi:10.1063/1.4941602

Title: Identification of the dominant photochemical pathways and mechanistic insights to the ultrafast ligand exchange of Fe(CO)₅ to Fe(CO)₄EtOH

Journal Article · Tue Feb 09 00:00:00 EST 2016 · Structural Dynamics

DOI:https://doi.org/10.1063/1.4941602· OSTI ID:1242357

Kunnus, K. ^[1]; Josefsson, I. ^[2]; Rajkovic, I. ^[3]; Schreck, S. ^[1]; Quevedo, W. ^[4]; Beye, M. ^[4]; Weniger, C. ^[4]; Grübel, S. ^[3]; Scholz, M. ^[3]; Nordlund, D. ^[5]; Zhang, W. ^[6]; Hartsock, R. W. ^[6]; Gaffney, K. J. ^[6]; Schlotter, W. F. ^[7]; Turner, J. J. ^[7]; Kennedy, B. ^[4]; Hennies, F. ^[8]; de Groot, F. M. F. ^[9]; Techert, S. ^[10]; Odelius, M. ^[2] more »

Helmholtz-Zentrum Berlin (HZB), (Germany). German Research Centre for Materials and Energy; Univ. Potsdam, Potsdam (Germany). Institut fur Physik und Astronomie
Stockholm Univ. (Sweden). Department of Physics
Max Planck Institute for Biophysical Chemistry, Am Fassberg, Gottingen (Germany)
Helmholtz-Zentrum Berlin (HZB), (Germany). German Research Centre for Materials and Energy
SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
SLAC National Accelerator Lab., Menlo Park, CA (United States). PULSE Institute
SLAC National Accelerator Lab., Menlo Park, CA (United States). Linac Coherent Light Source (LCLS)
MAX-lab, Lund (Sweden)
Utrecht Univ. Utrecht (Netherlands). Department of Chemistry
Max Planck Institute for Biophysical Chemistry, Am Fassberg, Gottingen (Germany); Gottingen Univ. (Germany); Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany)

Here, we utilized femtosecond time-resolved resonant inelastic X-ray scattering and ab initio theory to study the transient electronic structure and the photoinduced molecular dynamics of a model metal carbonyl photocatalyst Fe(CO)₅ in ethanol solution. We propose mechanistic explanation for the parallel ultrafast intra-molecular spin crossover and ligation of the Fe(CO)₄ which are observed following a charge transfer photoexcitation of Fe(CO)₅ as reported in our previous study. We find that branching of the reaction pathway likely happens in the ¹A₁ state of Fe(CO)₄. A sub-picosecond time constant of the spin crossover from ¹B₂ to ³B₂ is rationalized by the proposed ¹B₂ → ¹A₁ → ³B₂ mechanism. Ultrafast ligation of the ¹B₂ Fe(CO)₄ state is significantly faster than the spin-forbidden and diffusion limited ligation process occurring from the ³B₂ Fe(CO)₄ ground state that has been observed in the previous studies. We propose that the ultrafast ligation occurs via ¹B₂ → ¹A₁ → ¹A' Fe(CO)₄EtOH pathway and the time scale of the ¹A₁ Fe(CO)₄ state ligation is governed by the solute-solvent collision frequency. Our study emphasizes the importance of understanding the interaction of molecular excited states with the surrounding environment to explain the relaxation pathways of photoexcited metal carbonyls in solution.

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Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

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

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1242357

Alternate ID(s):: OSTI ID: 1335953

Journal Information:: Structural Dynamics, Vol. 3, Issue 4; ISSN 2329-7778

Publisher:: American Crystallographic Association/AIPCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 40 works

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Title: Identification of the dominant photochemical pathways and mechanistic insights to the ultrafast ligand exchange of Fe(CO)5 to Fe(CO)4EtOH

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Title: Identification of the dominant photochemical pathways and mechanistic insights to the ultrafast ligand exchange of Fe(CO)₅ to Fe(CO)₄EtOH