Structure-switching M3L2 Ir(III) coordination cages with photo-isomerising azo-aromatic linkers

Samuel Oldknow; Diego Rota Martir; Victoria E. Pritchard; Mark A. Blitz; Colin W.G. Fishwick; Eli Zysman-Colman; Michaele J. Hardie

doi:10.1039/c8sc03499k

Structure-switching M₃L₂ Ir(III) coordination cages with photo-isomerising azo-aromatic linkers

Samuel Oldknow, Diego Rota Martir, Victoria E. Pritchard, Mark A. Blitz, Colin W.G. Fishwick, Eli Zysman-Colman, Michaele J. Hardie^*

^*Corresponding author for this work

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

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Abstract

Cyclotriguaiacylene has been functionalised with 3- or 4-pyridyl-azo-phenyl groups to form a series of molecular hosts with three azobenzene-type groups that exhibit reversible photo-isomerisation. Reaction of the host molecules with [Ir(C^N)₂(NCMe)₂]⁺ where C^N is the cyclometallating 2-phenylpyridinato, 2-(4-methylphenyl)pyridinato or 2-(4,5,6-trifluorophenyl)pyridinato results in the self-assembly of a family of five different [{Ir(C^N)₂}₃(L)₂]³⁺ coordination cages. Photo-irradiation of each of the cages with a high energy laser results in E → Z photo-isomerisation of the pyridyl-azo-phenyl groups with up to 40% of groups isomerising. Isomerisation can be reversed by exposure to blue light. Thus, the cages show reversible structure-switching while maintaining their compositional integrity. This represents the largest photo-induced structural change yet reported for a structurally-integral component of a coordination cage. Energy minimised molecular models indicate a switched cage has a smaller internal space than the initial all-E isomer. The [Ir(C^N)₂(NCMe)₂]⁺ cages are weakly emissive, each with a deep blue luminescence at ca. 450 nm.

Original language	English
Pages (from-to)	8150-8159
Number of pages	10
Journal	Chemical Science
Volume	9
Issue number	42
Early online date	6 Sept 2018
DOIs	https://doi.org/10.1039/c8sc03499k
Publication status	Published - 14 Nov 2018

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10.1039/c8sc03499kLicence: CC BY

Oldknow_2018_Structure-switching_CC
Copyright © 2018 The Author(s). Open Access article. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
Final published version, 1.39 MBLicence: CC BY

Blue-Emitting TADF Materials: Blue-Emitting TADF Materials for OLEDs Based on a Lewis Acid-Containing Acceptor
Zysman-Colman, E. (PI)
The Leverhulme Trust
1/08/16 → 30/04/22
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

Data to support study "Structure-switching M3L2 Ir(III) coordination cages with photo-isomerising azo-aromatic groups"
Hardie, M. (Creator), Samuel, O. (Creator), Rota Martir, D. (Creator), Victoria, P. (Creator), Mark, B. (Creator), Colin, F. (Creator) & Zysman-Colman, E. (Creator), University of Leeds, 3 Sept 2018
DOI: 10.5518/438
Dataset
Structure-switching M3L2 Ir(III) coordination cages with photo-isomerising azo-aromatic linkers (crystallography data)
Oldknow, S. (Creator), Rota Martir, D. (Creator), Pritchard, V. E. (Creator), Blitz, M. (Creator), Fishwick, C. (Creator), Zysman-Colman, E. (Creator) & Hardie, M. J. (Creator), Cambridge Crystallographic Data Centre, 30 Jul 2018
https://dx.doi.org/10.5517/ccdc.csd.cc1zrllx and 3 more links, https://dx.doi.org/10.5517/ccdc.csd.cc1zrlmy, https://dx.doi.org/10.5517/ccdc.csd.cc20dnrv, https://dx.doi.org/10.5517/ccdc.csd.cc20dnsw (show fewer)
Dataset

Cite this

@article{8659a6dae9c94874a596c75b0b4531c3,

title = "Structure-switching M3L2 Ir(III) coordination cages with photo-isomerising azo-aromatic linkers",

abstract = "Cyclotriguaiacylene has been functionalised with 3- or 4-pyridyl-azo-phenyl groups to form a series of molecular hosts with three azobenzene-type groups that exhibit reversible photo-isomerisation. Reaction of the host molecules with [Ir(C^N)2(NCMe)2]+ where C^N is the cyclometallating 2-phenylpyridinato, 2-(4-methylphenyl)pyridinato or 2-(4,5,6-trifluorophenyl)pyridinato results in the self-assembly of a family of five different [{Ir(C^N)2}3(L)2]3+ coordination cages. Photo-irradiation of each of the cages with a high energy laser results in E → Z photo-isomerisation of the pyridyl-azo-phenyl groups with up to 40% of groups isomerising. Isomerisation can be reversed by exposure to blue light. Thus, the cages show reversible structure-switching while maintaining their compositional integrity. This represents the largest photo-induced structural change yet reported for a structurally-integral component of a coordination cage. Energy minimised molecular models indicate a switched cage has a smaller internal space than the initial all-E isomer. The [Ir(C^N)2(NCMe)2]+ cages are weakly emissive, each with a deep blue luminescence at ca. 450 nm.",

author = "Samuel Oldknow and Martir, {Diego Rota} and Pritchard, {Victoria E.} and Blitz, {Mark A.} and Fishwick, {Colin W.G.} and Eli Zysman-Colman and Hardie, {Michaele J.}",

note = "This work was supported by The Leverhulme Trust (RPG-2014-148), EPSRC (EP/M02105X/1, 1238852 (VEP), equipment grant EP/K039202/1). This work was carried out with support of Diamond Light Source (MT-10344).",

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doi = "10.1039/c8sc03499k",

language = "English",

volume = "9",

pages = "8150--8159",

journal = "Chemical Science",

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publisher = "Royal Society of Chemistry",

number = "42",

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TY - JOUR

T1 - Structure-switching M3L2 Ir(III) coordination cages with photo-isomerising azo-aromatic linkers

AU - Oldknow, Samuel

AU - Martir, Diego Rota

AU - Pritchard, Victoria E.

AU - Blitz, Mark A.

AU - Fishwick, Colin W.G.

AU - Zysman-Colman, Eli

AU - Hardie, Michaele J.

N1 - This work was supported by The Leverhulme Trust (RPG-2014-148), EPSRC (EP/M02105X/1, 1238852 (VEP), equipment grant EP/K039202/1). This work was carried out with support of Diamond Light Source (MT-10344).

PY - 2018/11/14

Y1 - 2018/11/14

N2 - Cyclotriguaiacylene has been functionalised with 3- or 4-pyridyl-azo-phenyl groups to form a series of molecular hosts with three azobenzene-type groups that exhibit reversible photo-isomerisation. Reaction of the host molecules with [Ir(C^N)2(NCMe)2]+ where C^N is the cyclometallating 2-phenylpyridinato, 2-(4-methylphenyl)pyridinato or 2-(4,5,6-trifluorophenyl)pyridinato results in the self-assembly of a family of five different [{Ir(C^N)2}3(L)2]3+ coordination cages. Photo-irradiation of each of the cages with a high energy laser results in E → Z photo-isomerisation of the pyridyl-azo-phenyl groups with up to 40% of groups isomerising. Isomerisation can be reversed by exposure to blue light. Thus, the cages show reversible structure-switching while maintaining their compositional integrity. This represents the largest photo-induced structural change yet reported for a structurally-integral component of a coordination cage. Energy minimised molecular models indicate a switched cage has a smaller internal space than the initial all-E isomer. The [Ir(C^N)2(NCMe)2]+ cages are weakly emissive, each with a deep blue luminescence at ca. 450 nm.

AB - Cyclotriguaiacylene has been functionalised with 3- or 4-pyridyl-azo-phenyl groups to form a series of molecular hosts with three azobenzene-type groups that exhibit reversible photo-isomerisation. Reaction of the host molecules with [Ir(C^N)2(NCMe)2]+ where C^N is the cyclometallating 2-phenylpyridinato, 2-(4-methylphenyl)pyridinato or 2-(4,5,6-trifluorophenyl)pyridinato results in the self-assembly of a family of five different [{Ir(C^N)2}3(L)2]3+ coordination cages. Photo-irradiation of each of the cages with a high energy laser results in E → Z photo-isomerisation of the pyridyl-azo-phenyl groups with up to 40% of groups isomerising. Isomerisation can be reversed by exposure to blue light. Thus, the cages show reversible structure-switching while maintaining their compositional integrity. This represents the largest photo-induced structural change yet reported for a structurally-integral component of a coordination cage. Energy minimised molecular models indicate a switched cage has a smaller internal space than the initial all-E isomer. The [Ir(C^N)2(NCMe)2]+ cages are weakly emissive, each with a deep blue luminescence at ca. 450 nm.

U2 - 10.1039/c8sc03499k

DO - 10.1039/c8sc03499k

M3 - Article

AN - SCOPUS:85056097784

SN - 2041-6520

VL - 9

SP - 8150

EP - 8159

JO - Chemical Science

JF - Chemical Science

IS - 42

ER -

Structure-switching M3L2 Ir(III) coordination cages with photo-isomerising azo-aromatic linkers

Abstract

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Blue-Emitting TADF Materials: Blue-Emitting TADF Materials for OLEDs Based on a Lewis Acid-Containing Acceptor

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

Datasets

Data to support study "Structure-switching M3L2 Ir(III) coordination cages with photo-isomerising azo-aromatic groups"

Structure-switching M3L2 Ir(III) coordination cages with photo-isomerising azo-aromatic linkers (crystallography data)

Cite this

Structure-switching M₃L₂ Ir(III) coordination cages with photo-isomerising azo-aromatic linkers