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Chemical control of competing electron transfer pathways in iron tetracyano-polypyridyl photosensitizers
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- Kunnus, Kristjan (författare)
- Stanford Univ, Stanford PULSE Inst, SLAC Natl Accelerator Lab, Menlo Pk, CA 94025 USA.
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- Li, Lin (författare)
- Uppsala universitet,Fysikalisk kemi,Stanford Univ, Stanford PULSE Inst, SLAC Natl Accelerator Lab, Menlo Pk, CA 94025 USA.
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- Titus, Charles (författare)
- Stanford Univ, Dept Phys, Stanford, CA 94305 USA.
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- Stanford Univ, Stanford PULSE Inst, SLAC Natl Accelerator Lab, Menlo Pk, CA 94025 USA Fysikalisk kemi (creator_code:org_t)
- 2020
- 2020
- Engelska.
- Ingår i: Chemical Science. - : ROYAL SOC CHEMISTRY. - 2041-6520 .- 2041-6539. ; 11:17, s. 4360-4373
- Tidskriftsartikel (refereegranskat)
Abstract
Ämnesord
Stäng
- Photoinduced intramolecular electron transfer dynamics following metal-to-ligand charge-transfer (MLCT) excitation of [Fe(CN)(4)(2,2 '-bipyridine)](2-) (1), [Fe(CN)(4)(2,3-bis(2-pyridyl)pyrazine)](2-) (2) and [Fe(CN)(4)(2,2 '-bipyrimidine)](2-) (3) were investigated in various solvents with static and time-resolved UV-Visible absorption spectroscopy and Fe 2p3d resonant inelastic X-ray scattering (RIXS). This series of polypyridyl ligands, combined with the strong solvatochromism of the complexes, enables the (MLCT)-M-1 vertical energy to be varied from 1.64 eV to 2.64 eV and the (MLCT)-M-3 lifetime to range from 180 fs to 67 ps. The (MLCT)-M-3 lifetimes in 1 and 2 decrease exponentially as the MLCT energy increases, consistent with electron transfer to the lowest energy triplet metal-centred ((MC)-M-3) excited state, as established by the Tanabe-Sugano analysis of the Fe 2p3d RIXS data. In contrast, the (MLCT)-M-3 lifetime in 3 changes non-monotonically with MLCT energy, exhibiting a maximum. This qualitatively distinct behaviour results from a competing (MLCT)-M-3 -> ground state (GS) electron transfer pathway that exhibits energy gap law behaviour. The (MLCT)-M-3 -> GS pathway involves nuclear tunnelling for the high-frequency polypyridyl breathing mode (h nu = 1530 cm(-1)), which is most displaced for complex 3, making this pathway significantly more efficient. Our study demonstrates that the excited state relaxation mechanism of Fe polypyridyl photosensitizers can be readily tuned by ligand and solvent environment. Furthermore, our study reveals that extending charge transfer lifetimes requires control of the relative energies of the (MLCT)-M-3 and the (MC)-M-3 states and suppression of the intramolecular distortion of the acceptor ligand in the (MLCT)-M-3 excited state.
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- NATURVETENSKAP -- Kemi -- Teoretisk kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences -- Theoretical Chemistry (hsv//eng)
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- Kunnus, Kristjan
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- Kjaer, Kasper S.
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