A Near Infra-Red Luminescent Cr(III) N-Heterocyclic Carbene Complex

Robert Jones; Rory A. Cowin; Iona Ivalo; Dimitri  Chekulaev; Thomas M. Roseveare; Craig Rice; Julia A. Weinstein; Paul Elliott; Paul Scattergood

doi:10.1021/acs.inorgchem.4c01270

A Near Infra-Red Luminescent Cr(III) N-Heterocyclic Carbene Complex

Robert Jones, Rory A. Cowin, Iona Ivalo, Dimitri Chekulaev, Thomas M. Roseveare, Craig Rice, Julia A. Weinstein, Paul Elliott, Paul Scattergood

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Abstract

Photoluminescent coordination complexes of Cr(III) are of interest as near-infrared spin-flip emitters. Here, we explore the preparation, electrochemistry, and photophysical properties of the first two examples of homoleptic N-heterocyclic carbene complexes of Cr(III), featuring 2,6-bis(imidazolyl)pyridine (ImPyIm) and 2-imidazolylpyridine (ImPy) ligands. The complex [Cr(ImPy)3]3+ displays luminescence at 803 nm on the microsecond time scale (13.7 μs) from a spin-flip doublet excited state, which transient absorption spectroscopy reveals to be populated within several picoseconds following photoexcitation. Conversely, [Cr(ImPyIm)2]3+ is nonemissive and has a ca. 500 ps excited-state lifetime.

Original language	English
Pages (from-to)	8526-8530
Number of pages	5
Journal	Inorganic Chemistry
Volume	63
Issue number	19
Early online date	2 May 2024
DOIs	https://doi.org/10.1021/acs.inorgchem.4c01270
Publication status	Published - 13 May 2024

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title = "A Near Infra-Red Luminescent Cr(III) N-Heterocyclic Carbene Complex",

abstract = "Photoluminescent coordination complexes of Cr(III) are of interest as near-infrared spin-flip emitters. Here, we explore the preparation, electrochemistry, and photophysical properties of the first two examples of homoleptic N-heterocyclic carbene complexes of Cr(III), featuring 2,6-bis(imidazolyl)pyridine (ImPyIm) and 2-imidazolylpyridine (ImPy) ligands. The complex [Cr(ImPy)3]3+ displays luminescence at 803 nm on the microsecond time scale (13.7 μs) from a spin-flip doublet excited state, which transient absorption spectroscopy reveals to be populated within several picoseconds following photoexcitation. Conversely, [Cr(ImPyIm)2]3+ is nonemissive and has a ca. 500 ps excited-state lifetime.",

keywords = "Cr(III), homoleptic N-heterocyclic carbene complexes, near-infrared (NIR)",

author = "Robert Jones and Cowin, {Rory A.} and Iona Ivalo and Dimitri Chekulaev and Roseveare, {Thomas M.} and Craig Rice and Weinstein, {Julia A.} and Paul Elliott and Paul Scattergood",

note = "Funding Information: P.A.S. acknowledges financial support from the Royal Society (RGS\\R2\\192292) and the Royal Society of Chemistry (RF19-2770) in addition to the Leverhulme Trust (RPG-2022-128). R.W.J. thanks the Engineering and Physical Sciences Research Council (EPSRC) for a doctoral studentship (EP/R513234/1). J.A.W., R.C., I.I.I., D.C., and T.M.R. thank the University of Sheffield for support and the EPSRC for a Capital Award to the Lord Porter Laser Laboratory. J.A.W and I.I.I. also acknowledge support from the EPSRC (EP/T012455/1). Publisher Copyright: {\textcopyright} 2024 The Authors. Published by American Chemical Society",

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doi = "10.1021/acs.inorgchem.4c01270",

language = "English",

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T1 - A Near Infra-Red Luminescent Cr(III) N-Heterocyclic Carbene Complex

AU - Jones, Robert

AU - Cowin, Rory A.

AU - Ivalo, Iona

AU - Chekulaev, Dimitri

AU - Roseveare, Thomas M.

AU - Rice, Craig

AU - Weinstein, Julia A.

AU - Elliott, Paul

AU - Scattergood, Paul

N1 - Funding Information: P.A.S. acknowledges financial support from the Royal Society (RGS\\R2\\192292) and the Royal Society of Chemistry (RF19-2770) in addition to the Leverhulme Trust (RPG-2022-128). R.W.J. thanks the Engineering and Physical Sciences Research Council (EPSRC) for a doctoral studentship (EP/R513234/1). J.A.W., R.C., I.I.I., D.C., and T.M.R. thank the University of Sheffield for support and the EPSRC for a Capital Award to the Lord Porter Laser Laboratory. J.A.W and I.I.I. also acknowledge support from the EPSRC (EP/T012455/1). Publisher Copyright: © 2024 The Authors. Published by American Chemical Society

PY - 2024/5/13

Y1 - 2024/5/13

N2 - Photoluminescent coordination complexes of Cr(III) are of interest as near-infrared spin-flip emitters. Here, we explore the preparation, electrochemistry, and photophysical properties of the first two examples of homoleptic N-heterocyclic carbene complexes of Cr(III), featuring 2,6-bis(imidazolyl)pyridine (ImPyIm) and 2-imidazolylpyridine (ImPy) ligands. The complex [Cr(ImPy)3]3+ displays luminescence at 803 nm on the microsecond time scale (13.7 μs) from a spin-flip doublet excited state, which transient absorption spectroscopy reveals to be populated within several picoseconds following photoexcitation. Conversely, [Cr(ImPyIm)2]3+ is nonemissive and has a ca. 500 ps excited-state lifetime.

AB - Photoluminescent coordination complexes of Cr(III) are of interest as near-infrared spin-flip emitters. Here, we explore the preparation, electrochemistry, and photophysical properties of the first two examples of homoleptic N-heterocyclic carbene complexes of Cr(III), featuring 2,6-bis(imidazolyl)pyridine (ImPyIm) and 2-imidazolylpyridine (ImPy) ligands. The complex [Cr(ImPy)3]3+ displays luminescence at 803 nm on the microsecond time scale (13.7 μs) from a spin-flip doublet excited state, which transient absorption spectroscopy reveals to be populated within several picoseconds following photoexcitation. Conversely, [Cr(ImPyIm)2]3+ is nonemissive and has a ca. 500 ps excited-state lifetime.

KW - Cr(III)

KW - homoleptic N-heterocyclic carbene complexes

KW - near-infrared (NIR)

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U2 - 10.1021/acs.inorgchem.4c01270

DO - 10.1021/acs.inorgchem.4c01270

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VL - 63

SP - 8526

EP - 8530

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 19

ER -

A Near Infra-Red Luminescent Cr(III) N-Heterocyclic Carbene Complex

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A Near Infra-Red Luminescent Cr(III) N-Heterocyclic Carbene Complex

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