Luminescence and reactivity of a charge-transfer excited iron complex with nanosecond lifetime

Kasper Skov Kjær; Nidhi Kaul; Om Prakash; Pavel Chábera; Nils W. Rosemann; Alireza Honarfar; Olga Gordivska; Lisa A. Fredin; Karl-Erik Bergquist; Lennart Häggström; Tore Ericsson; Linnea Lindh; Arkady Yartsev; Stenbjörn Styring; Ping Huang; Jens Uhlig; Jesper Bendix; Daniel Strand; Villy Sundström; Petter Persson; Reiner Lomoth; Kenneth Wärnmark

Luminescence and reactivity of a charge-transfer excited iron complex with nanosecond lifetime

Kasper Skov Kjær, Nidhi Kaul, Om Prakash, Pavel Chábera, Nils W. Rosemann, Alireza Honarfar, Olga Gordivska, Lisa A. Fredin, Karl-Erik Bergquist, Lennart Häggström, Tore Ericsson, Linnea Lindh, Arkady Yartsev, Stenbjörn Styring, Ping Huang, Jens Uhlig, Jesper Bendix, Daniel Strand, Villy Sundström, Petter PerssonReiner Lomoth, Kenneth Wärnmark

Department of Chemistry

85 Citations (Scopus)

Abstract

Iron’s abundance and rich coordination chemistry are potentially appealing features for photochemical applications. However, the photoexcitable charge-transfer states of most iron complexes are limited by picosecond or subpicosecond deactivation through low-lying metal-centered states, resulting in inefficient electron-transfer reactivity and complete lack of photoluminescence. In this study, we show that octahedral coordination of iron(III) by two mono-anionic facial tris-carbene ligands can markedly suppress such deactivation.The resulting complex [Fe(phtmeimb) ₂ ] ⁺ , where phtmeimb is {phenyl[tris(3-methylimidazol-1-ylidene)] borate} ⁻ , exhibits strong, visible, room temperature photoluminescence with a 2.0-nanosecond lifetime and 2% quantum yield via spin-allowed transition from a doublet ligand-to-metal charge-transfer ( ² LMCT) state to the doublet ground state. Reductive and oxidative electron-transfer reactions were observed for the ² LMCT state of [Fe(phtmeimb) ₂ ] ⁺ in bimolecular quenching studies with methylviologen and diphenylamine.

Original language	English
Journal	Science
Volume	363
Issue number	6424
Pages (from-to)	249-253
ISSN	0036-8075
Publication status	Published - 18 Jan 2019

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Kjær, K. S., Kaul, N., Prakash, O., Chábera, P., Rosemann, N. W., Honarfar, A., Gordivska, O., Fredin, L. A., Bergquist, K.-E., Häggström, L., Ericsson, T., Lindh, L., Yartsev, A., Styring, S., Huang, P., Uhlig, J., Bendix, J., Strand, D., Sundström, V., ... Wärnmark, K. (2019). Luminescence and reactivity of a charge-transfer excited iron complex with nanosecond lifetime. Science, 363(6424), 249-253. https://science.sciencemag.org/content/sci/363/6424/249.full.pdf

Kjær, KS, Kaul, N, Prakash, O, Chábera, P, Rosemann, NW, Honarfar, A, Gordivska, O, Fredin, LA, Bergquist, K-E, Häggström, L, Ericsson, T, Lindh, L, Yartsev, A, Styring, S, Huang, P, Uhlig, J, Bendix, J, Strand, D, Sundström, V, Persson, P, Lomoth, R & Wärnmark, K 2019, 'Luminescence and reactivity of a charge-transfer excited iron complex with nanosecond lifetime', Science, vol. 363, no. 6424, pp. 249-253. <https://science.sciencemag.org/content/sci/363/6424/249.full.pdf>

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title = "Luminescence and reactivity of a charge-transfer excited iron complex with nanosecond lifetime",

abstract = " Iron{\textquoteright}s abundance and rich coordination chemistry are potentially appealing features for photochemical applications. However, the photoexcitable charge-transfer states of most iron complexes are limited by picosecond or subpicosecond deactivation through low-lying metal-centered states, resulting in inefficient electron-transfer reactivity and complete lack of photoluminescence. In this study, we show that octahedral coordination of iron(III) by two mono-anionic facial tris-carbene ligands can markedly suppress such deactivation.The resulting complex [Fe(phtmeimb) 2 ] + , where phtmeimb is {phenyl[tris(3-methylimidazol-1-ylidene)] borate} − , exhibits strong, visible, room temperature photoluminescence with a 2.0-nanosecond lifetime and 2% quantum yield via spin-allowed transition from a doublet ligand-to-metal charge-transfer ( 2 LMCT) state to the doublet ground state. Reductive and oxidative electron-transfer reactions were observed for the 2 LMCT state of [Fe(phtmeimb) 2 ] + in bimolecular quenching studies with methylviologen and diphenylamine. ",

author = "Kj{\ae}r, {Kasper Skov} and Nidhi Kaul and Om Prakash and Pavel Ch{\'a}bera and Rosemann, {Nils W.} and Alireza Honarfar and Olga Gordivska and Fredin, {Lisa A.} and Karl-Erik Bergquist and Lennart H{\"a}ggstr{\"o}m and Tore Ericsson and Linnea Lindh and Arkady Yartsev and Stenbj{\"o}rn Styring and Ping Huang and Jens Uhlig and Jesper Bendix and Daniel Strand and Villy Sundstr{\"o}m and Petter Persson and Reiner Lomoth and Kenneth W{\"a}rnmark",

year = "2019",

month = jan,

day = "18",

language = "English",

volume = "363",

pages = "249--253",

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T1 - Luminescence and reactivity of a charge-transfer excited iron complex with nanosecond lifetime

AU - Kjær, Kasper Skov

AU - Kaul, Nidhi

AU - Prakash, Om

AU - Chábera, Pavel

AU - Rosemann, Nils W.

AU - Honarfar, Alireza

AU - Gordivska, Olga

AU - Fredin, Lisa A.

AU - Bergquist, Karl-Erik

AU - Häggström, Lennart

AU - Ericsson, Tore

AU - Lindh, Linnea

AU - Yartsev, Arkady

AU - Styring, Stenbjörn

AU - Huang, Ping

AU - Uhlig, Jens

AU - Bendix, Jesper

AU - Strand, Daniel

AU - Sundström, Villy

AU - Persson, Petter

AU - Lomoth, Reiner

AU - Wärnmark, Kenneth

PY - 2019/1/18

Y1 - 2019/1/18

N2 - Iron’s abundance and rich coordination chemistry are potentially appealing features for photochemical applications. However, the photoexcitable charge-transfer states of most iron complexes are limited by picosecond or subpicosecond deactivation through low-lying metal-centered states, resulting in inefficient electron-transfer reactivity and complete lack of photoluminescence. In this study, we show that octahedral coordination of iron(III) by two mono-anionic facial tris-carbene ligands can markedly suppress such deactivation.The resulting complex [Fe(phtmeimb) 2 ] + , where phtmeimb is {phenyl[tris(3-methylimidazol-1-ylidene)] borate} − , exhibits strong, visible, room temperature photoluminescence with a 2.0-nanosecond lifetime and 2% quantum yield via spin-allowed transition from a doublet ligand-to-metal charge-transfer ( 2 LMCT) state to the doublet ground state. Reductive and oxidative electron-transfer reactions were observed for the 2 LMCT state of [Fe(phtmeimb) 2 ] + in bimolecular quenching studies with methylviologen and diphenylamine.

AB - Iron’s abundance and rich coordination chemistry are potentially appealing features for photochemical applications. However, the photoexcitable charge-transfer states of most iron complexes are limited by picosecond or subpicosecond deactivation through low-lying metal-centered states, resulting in inefficient electron-transfer reactivity and complete lack of photoluminescence. In this study, we show that octahedral coordination of iron(III) by two mono-anionic facial tris-carbene ligands can markedly suppress such deactivation.The resulting complex [Fe(phtmeimb) 2 ] + , where phtmeimb is {phenyl[tris(3-methylimidazol-1-ylidene)] borate} − , exhibits strong, visible, room temperature photoluminescence with a 2.0-nanosecond lifetime and 2% quantum yield via spin-allowed transition from a doublet ligand-to-metal charge-transfer ( 2 LMCT) state to the doublet ground state. Reductive and oxidative electron-transfer reactions were observed for the 2 LMCT state of [Fe(phtmeimb) 2 ] + in bimolecular quenching studies with methylviologen and diphenylamine.

M3 - Journal article

C2 - 30498167

SN - 0036-8075

VL - 363

SP - 249

EP - 253

JO - Science

JF - Science

IS - 6424

ER -

Luminescence and reactivity of a charge-transfer excited iron complex with nanosecond lifetime

Abstract

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