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Unprecedented strongly panchromic absorption from proton switchable iridium(III) azoimidazolate complexes

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Henwood_et_al_Chemistry_A_European_Journal_CC.pdf (926.9Kb)
Date
12/2015
Author
Henwood, Adam Francis
Hu, Yue
Sajjad, Muhammad Tariq
Thalluri, Venkata Visveswara Gopala Krishna
Ghosh, Sanjay Sanatan
Cordes, David Bradford
Slawin, Alexandra Martha Zoya
Samuel, Ifor David William
Robertson, Neil
Zysman-Colman, Eli
Keywords
Iridium
OPV
Dye
Panchromic diazo ligand
QD Chemistry
DAS
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Abstract
Two novel heteroleptic iridium(III) complexes bearing an aryldiazoimidazole ligand are reported. These complexes differ structurally with respect to the protonation state of the imidazole ring, but can be independently accessed by varying the synthetic conditions. Their structures have been unequivocally confirmed by X-ray crystal structure analysis, with surprising differences in the structural parameters of the two complexes. The strongly absorbing nature of the free diazoimidazole ligand is enhanced in these iridium complexes, with the protonated cationic complex demonstrating extraordinarily strong panchromic absorption up to 700 nm. The absorption profile of the deprotonated neutral complex is blue-shifted by about 100 nm and thus the interconversion between the two complexes as a function of the acidity/basicity of the environment can be readily monitored by absorption spectroscopy. Theoretical calculations reveal the origins of these markedly different absorption properties. Finally, the protonated analogue has been targeted as an acceptor material for organic photovoltaic (OPV) applications and preliminary results are reported.
Citation
Henwood , A F , Hu , Y , Sajjad , M T , Thalluri , V V G K , Ghosh , S S , Cordes , D B , Slawin , A M Z , Samuel , I D W , Robertson , N & Zysman-Colman , E 2015 , ' Unprecedented strongly panchromic absorption from proton switchable iridium(III) azoimidazolate complexes ' , Chemistry - A European Journal , vol. 21 , no. 52 , pp. 19128-19135 . https://doi.org/10.1002/chem.201503546
Publication
Chemistry - A European Journal
Status
Peer reviewed
DOI
https://doi.org/10.1002/chem.201503546
ISSN
0947-6539
Type
Journal article
Rights
© 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
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  • University of St Andrews Research
URI
http://hdl.handle.net/10023/7794

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