Higher MLCT lifetime of carbene iron(<scp>ii</scp>) complexes by chelate ring expansion

Reuter, Thomas; Kruse, Ayla; Schoch, Roland; Lochbrunner, Stefan; Heinze, Katja

doi:10.1039/d1cc02173g

Cited by 29 publications

(32 citation statements)

References 38 publications

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“…It was rather argued that the larger ligand flexibility of bidentates, as compared to tridentate ligands, would facilitate structural re‐organisation needed for the 3 MLCT‐ 3 MC relaxation [40] . This conjecture was indirectly confirmed by time‐resolved studies on different Fe(II) complexes with structural rigidity [41,42] …”

Section: Background and Recent Achievementsmentioning

confidence: 96%

Ultrafast Spectroscopy of Fe(II) Complexes Designed for Solar‐Energy Conversion: Current Status and Open Questions

et al. 2022

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One major challenge of future sustainable photochemistry is to replace precious and rare transition metals in applications such as energy conversion or electroluminescence by earth‐abundant, cheap, and recyclable materials. This involves using coordination complexes of first row transition metals such as Cu, Cr, or Mn. In the case of iron, which is attractive due to its natural abundance, fundamental limitations imposed by the small ligand field splitting energy have recently been overcome. In this review article, we briefly summarize the present knowledge and understanding of the structure‐property relationships of Fe(II) and Fe(III) complexes with excited state lifetimes in the nanosecond range. However, our main focus is to examine to which extent the ultrafast spectroscopy methods used so far provided insight into the excited state structure and the photo‐induced dynamics of these complexes. Driven by the main question of how to spectroscopically, i. e. in energy and concentration, differentiate the population of ligand‐ vs. metal‐centered states, the hitherto less exploited ultrafast vibrational spectroscopy is suggested to provide valuable complementary insights.

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Section: Background and Recent Achievementsmentioning

confidence: 96%

Ultrafast Spectroscopy of Fe(II) Complexes Designed for Solar‐Energy Conversion: Current Status and Open Questions

et al. 2022

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“…The key problem is that the more contracted 3d-orbitals of Fe II experience a substantially weaker ligand field than the 4d-orbitals of Ru II (Figure a), and in classical octahedral polypyridine complexes the metal-centered 3 T 1g and 5 T 2g excited states (Figure a) are energetically below the lowest MLCT state. Consequently, relaxation from the MLCT to these MC states is typically ultrafast (Figure b). , The MC states can indeed be exploited for photoredox reactions though they are nonemissive. − Recently, there has been important progress in elongating the lifetimes of dark MLCT states, as well as in understanding their population and deactivation pathways. − Much of this work has been reviewed, ,− and since these compounds are nonluminescent, they are not considered further here.…”

Section: Mlct Emitters: 3d6 (Mni and Cr0) Complexes And A 3d8 (Niii) ...mentioning

confidence: 99%

Luminescent First-Row Transition Metal Complexes

Wegeberg

Wenger

2021

JACS Au

180

234

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Precious and rare elements have traditionally dominated inorganic photophysics and photochemistry, but now we are witnessing a paradigm shift toward cheaper and more abundant metals. Even though emissive complexes based on selected first-row transition metals have long been known, recent conceptual breakthroughs revealed that a much broader range of elements in different oxidation states are useable for this purpose. Coordination compounds of V, Cr, Mn, Fe, Co, Ni, and Cu now show electronically excited states with unexpected reactivity and photoluminescence behavior. Aside from providing a compact survey of the recent conceptual key advances in this dynamic field, our Perspective identifies the main design strategies that enabled the discovery of fundamentally new types of 3d-metal-based luminophores and photosensitizers operating in solution at room temperature.

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“…To overcome this issue, the use of σ-donor or π-accepting ligands, as well as rigid structures can help achieve longer 3 MLCT lifetimes. 73 For a more detailed analysis, we highly recommend the review by Wenger and co-workers which describes the challenges associated with iron compared to ruthenium. 74…”

Section: Phototoxic First-row Transition Metal Complexesmentioning

confidence: 99%

“…To overcome this issue, the use of s-donor or p-accepting ligands, as well as rigid structures can help achieve longer 3 MLCT lifetimes. 73 For a more detailed analysis, we highly recommend the review by Wenger and co-workers which describes the challenges associated with iron compared to ruthenium. 74 Although a wide variety of iron oxidation states can exist in complexes -from Fe(0) to Fe(VI) -, the ferrous (+2) and ferric (+3) states are most frequently used.…”

Section: Ironmentioning

confidence: 99%

Phototherapeutic anticancer strategies with first-row transition metal complexes: a critical review

2022

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Higher MLCT lifetime of carbene iron(ii) complexes by chelate ring expansion

Abstract: High octahedricity and rigidity enable the high 9.2 ps 3MLCT lifetime of the iron(ii) complex [Fe(dpmi)2]2+ possessing only two carbene donor sites.

Cited by 29 publications

References 38 publications

Ultrafast Spectroscopy of Fe(II) Complexes Designed for Solar‐Energy Conversion: Current Status and Open Questions

Ultrafast Spectroscopy of Fe(II) Complexes Designed for Solar‐Energy Conversion: Current Status and Open Questions

Luminescent First-Row Transition Metal Complexes

Phototherapeutic anticancer strategies with first-row transition metal complexes: a critical review

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