mer-Ir(pmp)3 as a strongly photoreducing and stable Ir(C^C)3 photocatalyst for metallaphotoredox catalysis

Máire Griffin; Eli Zysman-Colman

doi:10.1039/D6QO00086J

mer-Ir(pmp)₃ as a strongly photoreducing and stable Ir(C^C)₃ photocatalyst for metallaphotoredox catalysis

Máire Griffin
, Eli Zysman-Colman^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

Abstract

Here we report a new homoleptic Ir(NHC) photocatalyst, mer-Ir(pmp)₃ which is the first Ir(C^C)3 photocatalyst to operate effectively using excitation sources peaking in the visible (λ_exc = 427, 440 and 456 nm). In line with previously reported Ir(C^C)3 photocatalysts, mer-Ir(pmp)₃ is a potent photoreductant, reducing substrates up to E_red = −2.7 V vs. SCE and energy transfer catalyst, sensitizing substrates up to E_T = 3.00 eV. Furthermore, mer-Ir(pmp)₃ can engage in dual nickel photoredox catalysis on account of its red-shifted absorption spectrum and anodically shifted redox potentials. Compared to the literature-known photocatalysts, [Ir(dF(CF₃)ppy)₂(dtbbpy)]PF₆, 4CzIPN and [Ru(bpy)₃](PF₆)₂, mer-Ir(pmp)₃ achieves competitive or improved yields for the amination of aryl bromides and exhibits good photostability across a range of different conditions.

Original language	English
Pages (from-to)	2707–2718
Number of pages	12
Journal	Organic Chemistry Frontiers
Volume	13
Issue number	9
Early online date	19 Mar 2026
DOIs	https://doi.org/10.1039/D6QO00086J
Publication status	Published - 5 May 2026

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Griffin_2026_OCF_mer-Ir(pmp)3-photocatalyst_AAM_CCBY
Copyright © 2026 the Authors. This work has been made available online in accordance with the University of St Andrews Open Access policy. This accepted manuscript is distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited. The final published version of this work is available at https://doi.org/10.1039/D6QO00086J
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Allan Watson Programme Grant: Boron: Beyond the Reagent
Watson, A. (PI), Morris, R. (CoI), Smith, A. (CoI) & Zysman-Colman, E. (CoI)
UK Research and Innovation
1/05/23 → 30/04/28
Project: Standard
H2020 MSC-ITN Eli Zysman-Colman: Photocatalysis as a tool for synthetic organic chemistry (PhotoReAct)
Zysman-Colman, E. (PI)
Joint Research Centre European Commission
1/01/21 → 31/12/24
Project: Standard
Blue-Emitting Phospors: Blue-emitting Phosphors for Solid State Lighting Applications
Zysman-Colman, E. (PI)
EPSRC
1/06/15 → 30/09/19
Project: Standard

Development of strongly photoreducing, high triplet energy Iridium(III) NHC complexes for use in photocatalysis (thesis data)
Griffin, M. A. (Creator) & Zysman-Colman, E. (Supervisor), University of St Andrews, 14 May 2027
DOI: 10.17630/cf02cd3d-976d-417d-813e-865d83a306cf
Dataset: Thesis dataset
Bringing Ir(C^C)3 Photocatalysts into the visible: mer-Ir(pmp)3 as a strongly photoreducing and stable photocatalyst for metallaphotoredox catalysis (dataset)
Griffin, M. A. (Creator) & Zysman-Colman, E. (Creator), University of St Andrews, 25 Mar 2026
DOI: 10.17630/e3a52013-7ffe-463f-832e-e84b783d2b90
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Development of strongly photoreducing, high triplet energy iridium(III) NHC complexes for use in photocatalysis
Griffin, M. A. (Author), Zysman-Colman, E. (Supervisor), 2 Jul 2026
Student thesis: Doctoral Thesis (PhD)

Cite this

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title = "mer-Ir(pmp)3 as a strongly photoreducing and stable Ir(C\textasciicircum{}C)3 photocatalyst for metallaphotoredox catalysis",

abstract = "Here we report a new homoleptic Ir(NHC) photocatalyst, mer-Ir(pmp)3 which is the first Ir(C\textasciicircum{}C)3 photocatalyst to operate effectively using excitation sources peaking in the visible (λexc = 427, 440 and 456 nm). In line with previously reported Ir(C\textasciicircum{}C)3 photocatalysts, mer-Ir(pmp)3 is a potent photoreductant, reducing substrates up to Ered = −2.7 V vs. SCE and energy transfer catalyst, sensitizing substrates up to ET = 3.00 eV. Furthermore, mer-Ir(pmp)3 can engage in dual nickel photoredox catalysis on account of its red-shifted absorption spectrum and anodically shifted redox potentials. Compared to the literature-known photocatalysts, [Ir(dF(CF3)ppy)2(dtbbpy)]PF6, 4CzIPN and [Ru(bpy)3](PF6)2, mer-Ir(pmp)3 achieves competitive or improved yields for the amination of aryl bromides and exhibits good photostability across a range of different conditions.",

author = "M{\'a}ire Griffin and Eli Zysman-Colman",

note = "Funding: The authors thank Johnson Matthey for financial support in the form of an iCASE award (PhD studentship to M. G.). The authors thank EPSRC for financial support (EP/W522259/1, EP/W007517/1 and EP/M02105X/1). We would like to thank the European Union H2020 research and innovation program for the funding under the Marie Sk{\l}odowska-Curie Grant Agreement (PhotoReAct, No. 956324).",

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month = may,

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doi = "10.1039/D6QO00086J",

language = "English",

volume = "13",

pages = "2707–2718",

journal = "Organic Chemistry Frontiers",

issn = "2052-4129",

publisher = "Royal Society of Chemistry",

number = "9",

}

TY - JOUR

T1 - mer-Ir(pmp)3 as a strongly photoreducing and stable Ir(C^C)3 photocatalyst for metallaphotoredox catalysis

AU - Griffin, Máire

AU - Zysman-Colman, Eli

N1 - Funding: The authors thank Johnson Matthey for financial support in the form of an iCASE award (PhD studentship to M. G.). The authors thank EPSRC for financial support (EP/W522259/1, EP/W007517/1 and EP/M02105X/1). We would like to thank the European Union H2020 research and innovation program for the funding under the Marie Skłodowska-Curie Grant Agreement (PhotoReAct, No. 956324).

PY - 2026/5/5

Y1 - 2026/5/5

N2 - Here we report a new homoleptic Ir(NHC) photocatalyst, mer-Ir(pmp)3 which is the first Ir(C^C)3 photocatalyst to operate effectively using excitation sources peaking in the visible (λexc = 427, 440 and 456 nm). In line with previously reported Ir(C^C)3 photocatalysts, mer-Ir(pmp)3 is a potent photoreductant, reducing substrates up to Ered = −2.7 V vs. SCE and energy transfer catalyst, sensitizing substrates up to ET = 3.00 eV. Furthermore, mer-Ir(pmp)3 can engage in dual nickel photoredox catalysis on account of its red-shifted absorption spectrum and anodically shifted redox potentials. Compared to the literature-known photocatalysts, [Ir(dF(CF3)ppy)2(dtbbpy)]PF6, 4CzIPN and [Ru(bpy)3](PF6)2, mer-Ir(pmp)3 achieves competitive or improved yields for the amination of aryl bromides and exhibits good photostability across a range of different conditions.

AB - Here we report a new homoleptic Ir(NHC) photocatalyst, mer-Ir(pmp)3 which is the first Ir(C^C)3 photocatalyst to operate effectively using excitation sources peaking in the visible (λexc = 427, 440 and 456 nm). In line with previously reported Ir(C^C)3 photocatalysts, mer-Ir(pmp)3 is a potent photoreductant, reducing substrates up to Ered = −2.7 V vs. SCE and energy transfer catalyst, sensitizing substrates up to ET = 3.00 eV. Furthermore, mer-Ir(pmp)3 can engage in dual nickel photoredox catalysis on account of its red-shifted absorption spectrum and anodically shifted redox potentials. Compared to the literature-known photocatalysts, [Ir(dF(CF3)ppy)2(dtbbpy)]PF6, 4CzIPN and [Ru(bpy)3](PF6)2, mer-Ir(pmp)3 achieves competitive or improved yields for the amination of aryl bromides and exhibits good photostability across a range of different conditions.

U2 - 10.1039/D6QO00086J

DO - 10.1039/D6QO00086J

M3 - Article

SN - 2052-4129

VL - 13

SP - 2707

EP - 2718

JO - Organic Chemistry Frontiers

JF - Organic Chemistry Frontiers

IS - 9

ER -

mer-Ir(pmp)3 as a strongly photoreducing and stable Ir(C^C)3 photocatalyst for metallaphotoredox catalysis

Abstract

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Projects

Allan Watson Programme Grant: Boron: Beyond the Reagent

H2020 MSC-ITN Eli Zysman-Colman: Photocatalysis as a tool for synthetic organic chemistry (PhotoReAct)

Blue-Emitting Phospors: Blue-emitting Phosphors for Solid State Lighting Applications

Datasets

Development of strongly photoreducing, high triplet energy Iridium(III) NHC complexes for use in photocatalysis (thesis data)

Bringing Ir(C^C)3 Photocatalysts into the visible: mer-Ir(pmp)3 as a strongly photoreducing and stable photocatalyst for metallaphotoredox catalysis (dataset)

Student theses

Development of strongly photoreducing, high triplet energy iridium(III) NHC complexes for use in photocatalysis

Cite this

mer-Ir(pmp)₃ as a strongly photoreducing and stable Ir(C^C)₃ photocatalyst for metallaphotoredox catalysis