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Title: Observation of parallel intersystem crossing and charge transfer-state dynamics in [Fe(bpy)3]2+ from ultrafast 2D electronic spectroscopy

Journal Article · · Chemical Science
DOI: https://doi.org/10.1039/d3sc02613b · OSTI ID:2205136
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3];  [4]; ORCiD logo [5];  [4];  [1]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [1]
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
  2. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Boston Univ., MA (United States)
  3. North Carolina State University, Raleigh, NC (United States)
  4. Michigan State Univ., East Lansing, MI (United States)
  5. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Univ. of California, Berkeley, CA (United States)
+ Show Author Affiliations

Transition metal-based charge-transfer complexes represent a broad class of inorganic compounds with diverse photochemical applications. Charge-transfer complexes based on earth-abundant elements have been of increasing interest, particularly the canonical [Fe(bpy)3]2+. Photoexcitation into the singlet metal–ligand charge transfer (1MLCT) state is followed by relaxation first to the ligand-field manifold and then to the ground state. While these dynamics have been well-studied, processes within the MLCT manifold that facilitate and/or compete with relaxation have been more elusive. We applied ultrafast two-dimensional electronic spectroscopy (2DES) to disentangle the dynamics immediately following MLCT excitation of this compound. First, dynamics ascribed to relaxation out of the initially formed 1MLCT state was found to correlate with the inertial response time of the solvent. Second, the additional dimension of the 2D spectra revealed a peak consistent with a ~20 fs 1MLCT → 3MLCT intersystem crossing process. These two observations indicate that the complex simultaneously undergoes intersystem crossing and direct conversion to ligand-field state(s). Resolution of these parallel pathways in this prototypical earth-abundant complex highlights the ability of 2DES to deconvolve the otherwise obscured excited-state dynamics of charge-transfer complexes.

Research Organization:
North Carolina State University, Raleigh, NC (United States); Michigan State Univ., East Lansing, MI (United States); Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Energy Frontier Research Centers (EFRC) (United States). Bio-inspired Light-Escalated Chemistry (BioLEC)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE
Grant/Contract Number:
SC0019370
OSTI ID:
2205136
Alternate ID(s):
OSTI ID: 2280835
Journal Information:
Chemical Science, Vol. 14, Issue 45; ISSN 2041-6520
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
charge-transfer
intersystem crossing
photoredox catalysis
2-dimensional electronic spectroscopy
first row transition metals