A low-spin Fe(III) complex with 100-ps ligand-to-metal charge transfer photoluminescence

Pavel Chábera; Yizhu Liu; Om Prakash; Erling Thyrhaug; Amal El Nahhas; Alireza Honarfar; Sofia Essén; Lisa A. Fredin; Tobias C. B. Harlang; Kasper Skov Kjær; Karsten Handrup; Fredric Ericson; Hideyuki Tatsuno; Kelsey Morgan; Joachim Schnadt; Lennart Haggstrom; Tore Ericsson; Adam Sobkowiak; Sven Lidin; Ping Huang; Stenbjorn Styring; Jens Uhlig; Jesper Bendix; Reiner Lomoth; Villy Sundstrom; Petter Persson; Kenneth Warnmark

doi:10.1038/nature21430

A low-spin Fe(III) complex with 100-ps ligand-to-metal charge transfer photoluminescence

Pavel Chábera, Yizhu Liu, Om Prakash, Erling Thyrhaug, Amal El Nahhas, Alireza Honarfar, Sofia Essén, Lisa A. Fredin, Tobias C. B. Harlang, Kasper Skov Kjær, Karsten Handrup, Fredric Ericson, Hideyuki Tatsuno, Kelsey Morgan, Joachim Schnadt, Lennart Haggstrom, Tore Ericsson, Adam Sobkowiak, Sven Lidin, Ping HuangStenbjorn Styring, Jens Uhlig, Jesper Bendix, Reiner Lomoth, Villy Sundstrom, Petter Persson, Kenneth Warnmark

Department of Chemistry

144 Citations (Scopus)

Abstract

Transition-metal complexes are used as photosensitizers1, in light-emitting diodes, for biosensing and in photocatalysis2. A key feature in these applications is excitation from the ground state to a charge-transfer state3, 4; the long charge-transfer-state lifetimes typical for complexes of ruthenium5 and other precious metals are often essential to ensure high performance. There is much interest in replacing these scarce elements with Earth-abundant metals, with iron6 and copper7 being particularly attractive owing to their low cost and non-toxicity. But despite the exploration of innovative molecular designs6, 8, 9, 10, it remains a formidable scientific challenge11 to access Earth-abundant transition-metal complexes with long-lived charge-transfer excited states. No known iron complexes are considered12 photoluminescent at room temperature, and their rapid excited-state deactivation precludes their use as photosensitizers13, 14, 15. Here we present the iron complex [Fe(btz)3]3+ (where btz is 3,3′-dimethyl-1,1′-bis(p-tolyl)-4,4′-bis(1,2,3-triazol-5-ylidene)), and show that the superior σ-donor and π-acceptor electron properties of the ligand stabilize the excited state sufficiently to realize a long charge-transfer lifetime of 100 picoseconds (ps) and room-temperature photoluminescence. This species is a low-spin Fe(iii) d5 complex, and emission occurs from a long-lived doublet ligand-to-metal charge-transfer (2LMCT) state that is rarely seen for transition-metal complexes4, 16, 17. The absence of intersystem crossing, which often gives rise to large excited-state energy losses in transition-metal complexes, enables the observation of spin-allowed emission directly to the ground state and could be exploited as an increased driving force in photochemical reactions on surfaces. These findings suggest that appropriate design strategies can deliver new iron-based materials for use as light emitters and photosensitizers

Original language	English
Journal	Nature
Volume	543
Issue number	7647
Pages (from-to)	695-699
Number of pages	5
ISSN	0028-0836
DOIs	https://doi.org/10.1038/nature21430
Publication status	Published - 29 Mar 2017

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Chábera, P., Liu, Y., Prakash, O., Thyrhaug, E., El Nahhas, A., Honarfar, A., Essén, S., Fredin, L. A., Harlang, T. C. B., Kjær, K. S., Handrup, K., Ericson, F., Tatsuno, H., Morgan, K., Schnadt, J., Haggstrom, L., Ericsson, T., Sobkowiak, A., Lidin, S., ... Warnmark, K. (2017). A low-spin Fe(III) complex with 100-ps ligand-to-metal charge transfer photoluminescence. Nature, 543(7647), 695-699. https://doi.org/10.1038/nature21430

Chábera, P, Liu, Y, Prakash, O, Thyrhaug, E, El Nahhas, A, Honarfar, A, Essén, S, Fredin, LA, Harlang, TCB, Kjær, KS, Handrup, K, Ericson, F, Tatsuno, H, Morgan, K, Schnadt, J, Haggstrom, L, Ericsson, T, Sobkowiak, A, Lidin, S, Huang, P, Styring, S, Uhlig, J, Bendix, J, Lomoth, R, Sundstrom, V, Persson, P & Warnmark, K 2017, 'A low-spin Fe(III) complex with 100-ps ligand-to-metal charge transfer photoluminescence', Nature, vol. 543, no. 7647, pp. 695-699. https://doi.org/10.1038/nature21430

@article{cbeacc2749cb47b4b261d4e8fbc8d714,

title = "A low-spin Fe(III) complex with 100-ps ligand-to-metal charge transfer photoluminescence",

abstract = "Transition-metal complexes are used as photosensitizers1, in light-emitting diodes, for biosensing and in photocatalysis2. A key feature in these applications is excitation from the ground state to a charge-transfer state3, 4; the long charge-transfer-state lifetimes typical for complexes of ruthenium5 and other precious metals are often essential to ensure high performance. There is much interest in replacing these scarce elements with Earth-abundant metals, with iron6 and copper7 being particularly attractive owing to their low cost and non-toxicity. But despite the exploration of innovative molecular designs6, 8, 9, 10, it remains a formidable scientific challenge11 to access Earth-abundant transition-metal complexes with long-lived charge-transfer excited states. No known iron complexes are considered12 photoluminescent at room temperature, and their rapid excited-state deactivation precludes their use as photosensitizers13, 14, 15. Here we present the iron complex [Fe(btz)3]3+ (where btz is 3,3′-dimethyl-1,1′-bis(p-tolyl)-4,4′-bis(1,2,3-triazol-5-ylidene)), and show that the superior σ-donor and π-acceptor electron properties of the ligand stabilize the excited state sufficiently to realize a long charge-transfer lifetime of 100 picoseconds (ps) and room-temperature photoluminescence. This species is a low-spin Fe(iii) d5 complex, and emission occurs from a long-lived doublet ligand-to-metal charge-transfer (2LMCT) state that is rarely seen for transition-metal complexes4, 16, 17. The absence of intersystem crossing, which often gives rise to large excited-state energy losses in transition-metal complexes, enables the observation of spin-allowed emission directly to the ground state and could be exploited as an increased driving force in photochemical reactions on surfaces. These findings suggest that appropriate design strategies can deliver new iron-based materials for use as light emitters and photosensitizers",

author = "Pavel Ch{\'a}bera and Yizhu Liu and Om Prakash and Erling Thyrhaug and {El Nahhas}, Amal and Alireza Honarfar and Sofia Ess{\'e}n and Fredin, {Lisa A.} and Harlang, {Tobias C. B.} and Kj{\ae}r, {Kasper Skov} and Karsten Handrup and Fredric Ericson and Hideyuki Tatsuno and Kelsey Morgan and Joachim Schnadt and Lennart Haggstrom and Tore Ericsson and Adam Sobkowiak and Sven Lidin and Ping Huang and Stenbjorn Styring and Jens Uhlig and Jesper Bendix and Reiner Lomoth and Villy Sundstrom and Petter Persson and Kenneth Warnmark",

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T1 - A low-spin Fe(III) complex with 100-ps ligand-to-metal charge transfer photoluminescence

AU - Chábera, Pavel

AU - Liu, Yizhu

AU - Prakash, Om

AU - Thyrhaug, Erling

AU - El Nahhas, Amal

AU - Honarfar, Alireza

AU - Essén, Sofia

AU - Fredin, Lisa A.

AU - Harlang, Tobias C. B.

AU - Kjær, Kasper Skov

AU - Handrup, Karsten

AU - Ericson, Fredric

AU - Tatsuno, Hideyuki

AU - Morgan, Kelsey

AU - Schnadt, Joachim

AU - Haggstrom, Lennart

AU - Ericsson, Tore

AU - Sobkowiak, Adam

AU - Lidin, Sven

AU - Huang, Ping

AU - Styring, Stenbjorn

AU - Uhlig, Jens

AU - Bendix, Jesper

AU - Lomoth, Reiner

AU - Sundstrom, Villy

AU - Persson, Petter

AU - Warnmark, Kenneth

PY - 2017/3/29

Y1 - 2017/3/29

N2 - Transition-metal complexes are used as photosensitizers1, in light-emitting diodes, for biosensing and in photocatalysis2. A key feature in these applications is excitation from the ground state to a charge-transfer state3, 4; the long charge-transfer-state lifetimes typical for complexes of ruthenium5 and other precious metals are often essential to ensure high performance. There is much interest in replacing these scarce elements with Earth-abundant metals, with iron6 and copper7 being particularly attractive owing to their low cost and non-toxicity. But despite the exploration of innovative molecular designs6, 8, 9, 10, it remains a formidable scientific challenge11 to access Earth-abundant transition-metal complexes with long-lived charge-transfer excited states. No known iron complexes are considered12 photoluminescent at room temperature, and their rapid excited-state deactivation precludes their use as photosensitizers13, 14, 15. Here we present the iron complex [Fe(btz)3]3+ (where btz is 3,3′-dimethyl-1,1′-bis(p-tolyl)-4,4′-bis(1,2,3-triazol-5-ylidene)), and show that the superior σ-donor and π-acceptor electron properties of the ligand stabilize the excited state sufficiently to realize a long charge-transfer lifetime of 100 picoseconds (ps) and room-temperature photoluminescence. This species is a low-spin Fe(iii) d5 complex, and emission occurs from a long-lived doublet ligand-to-metal charge-transfer (2LMCT) state that is rarely seen for transition-metal complexes4, 16, 17. The absence of intersystem crossing, which often gives rise to large excited-state energy losses in transition-metal complexes, enables the observation of spin-allowed emission directly to the ground state and could be exploited as an increased driving force in photochemical reactions on surfaces. These findings suggest that appropriate design strategies can deliver new iron-based materials for use as light emitters and photosensitizers

AB - Transition-metal complexes are used as photosensitizers1, in light-emitting diodes, for biosensing and in photocatalysis2. A key feature in these applications is excitation from the ground state to a charge-transfer state3, 4; the long charge-transfer-state lifetimes typical for complexes of ruthenium5 and other precious metals are often essential to ensure high performance. There is much interest in replacing these scarce elements with Earth-abundant metals, with iron6 and copper7 being particularly attractive owing to their low cost and non-toxicity. But despite the exploration of innovative molecular designs6, 8, 9, 10, it remains a formidable scientific challenge11 to access Earth-abundant transition-metal complexes with long-lived charge-transfer excited states. No known iron complexes are considered12 photoluminescent at room temperature, and their rapid excited-state deactivation precludes their use as photosensitizers13, 14, 15. Here we present the iron complex [Fe(btz)3]3+ (where btz is 3,3′-dimethyl-1,1′-bis(p-tolyl)-4,4′-bis(1,2,3-triazol-5-ylidene)), and show that the superior σ-donor and π-acceptor electron properties of the ligand stabilize the excited state sufficiently to realize a long charge-transfer lifetime of 100 picoseconds (ps) and room-temperature photoluminescence. This species is a low-spin Fe(iii) d5 complex, and emission occurs from a long-lived doublet ligand-to-metal charge-transfer (2LMCT) state that is rarely seen for transition-metal complexes4, 16, 17. The absence of intersystem crossing, which often gives rise to large excited-state energy losses in transition-metal complexes, enables the observation of spin-allowed emission directly to the ground state and could be exploited as an increased driving force in photochemical reactions on surfaces. These findings suggest that appropriate design strategies can deliver new iron-based materials for use as light emitters and photosensitizers

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DO - 10.1038/nature21430

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SN - 0028-0836

VL - 543

SP - 695

EP - 699

JO - Nature

JF - Nature

IS - 7647

ER -

A low-spin Fe(III) complex with 100-ps ligand-to-metal charge transfer photoluminescence

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