4.8 Article

Reduction of Electron Repulsion in Highly Covalent Fe-Amido Complexes Counteracts the Impact of a Weak Ligand Field on Excited-State Ordering

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JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 143, 期 49, 页码 20645-20656

出版社

AMER CHEMICAL SOC
DOI: 10.1021/jacs.1c06429

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资金

  1. Natural Sciences Engineering Research Council of Canada [RGPIN-2014-03733]
  2. Research Manitoba [32146]
  3. U.S. Department of Energy, Office of Science, Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division [DE-AC02-76SF00515]
  4. U.S. DOE Office of Science User Facility [DE-AC02-05CH11231]
  5. Canadian Foundation for Innovation [32146]

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Accessing panchromatic absorption and long-lived charge-transfer (CT) excited states is crucial for developing abundant-metal molecular photosensitizers. This study presents an aerobically stable Fe(II) complex with panchromatic absorption and a 3 ns excited-state lifetime, demonstrating the importance of metal-ligand covalency in elongating excited state lifetimes. The findings highlight a novel design principle for extending excited state lifetimes in abundant metal photosensitizers.
The ability to access panchromatic absorption and long-lived charge-transfer (CT) excited states is critical to the pursuit of abundant-metal molecular photosensitizers. Fe(II) complexes supported by benzannulated diarylamido ligands have been reported to broadly absorb visible light with nanosecond CT excited state lifetimes, but as amido donors exert a weak ligand field, this defies conventional photosensitizer design principles. Here, we report an aerobically stable Fe(II) complex of a phenanthridine/quinoline diarylamido ligand, Fe(L-Cl)(2), with panchromatic absorption and a 3 ns excited-state lifetime. Using X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) at the Fe L-edge and N K-edge, we experimentally validate the strong Fe-N-amido orbital mixing in Fe(L-Cl)(2) responsible for the panchromatic absorption and demonstrate a previously unreported competition between ligand-field strength and metal-ligand (Fe-N-amido) covalency that stabilizes the (CT)-C-3 state over the lowest energy triplet metal-centered ((MC)-M-3) state in the ground-state geometry. Single-crystal X-ray diffraction (XRD) and density functional theory (DFT) suggest that formation of this CT state depopulates an orbital with Fe-N-amido antibonding character, causing metal-ligand bonds to contract and accentuating the geometric differences between CT and MC excited states. These effects diminish the driving force for electron transfer to metal-centered excited states and increase the intramolecular reorganization energy, critical properties for extending the lifetime of CT excited states. These findings highlight metal-ligand covalency as a novel design principle for elongating excited state lifetimes in abundant metal photosensitizers.

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