A rapidly-reversible absorptive and emissive vapochromic Pt(II) pincer-based chemical sensor

M. J. Bryant; J. M. Skelton; L. E. Hatcher; C. Stubbs; E. Madrid; A. R. Pallipurath; L. H. Thomas; C. H. Woodall; J. Christensen; S. Fuertes; T. P. Robinson; C. M. Beavers; S. J. Teat; M. R. Warren; F. Pradaux-Caggiano; A. Walsh; F. Marken; D. R. Carbery; S. C. Parker; N. B. McKeown; R. Malpass-Evans; M. Carta; P. R. Raithby

doi:10.1038/s41467-017-01941-2

A rapidly-reversible absorptive and emissive vapochromic Pt(II) pincer-based chemical sensor

M. J. Bryant, J. M. Skelton, L. E. Hatcher, C. Stubbs, E. Madrid, A. R. Pallipurath, L. H. Thomas, C. H. Woodall, J. Christensen, S. Fuertes, T. P. Robinson, C. M. Beavers, S. J. Teat, M. R. Warren, F. Pradaux-Caggiano, A. Walsh, F. Marken, D. R. Carbery, S. C. Parker, N. B. McKeownR. Malpass-Evans, M. Carta, P. R. Raithby

Department of Physics

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

88 Scopus citations

Abstract

Selective, robust and cost-effective chemical sensors for detecting small volatile-organic compounds (VOCs) have widespread applications in industry, healthcare and environmental monitoring. Here we design a Pt(II) pincer-Type material with selective absorptive and emissive responses to methanol and water. The yellow anhydrous form converts reversibly on a subsecond timescale to a red hydrate in the presence of parts-per-Thousand levels of atmospheric water vapour. Exposure to methanol induces a similarly-rapid and reversible colour change to a blue methanol solvate. Stable smart coatings on glass demonstrate robust switching over 10⁴ cycles, and flexible microporous polymer membranes incorporating microcrystals of the complex show identical vapochromic behaviour. The rapid vapochromic response can be rationalised from the crystal structure, and in combination with quantum-chemical modelling, we provide a complete microscopic picture of the switching mechanism. We discuss how this multiscale design approach can be used to obtain new compounds with tailored VOC selectivity and spectral responses.

Original language	English
Article number	1800
Journal	Nature Communications
Volume	8
Issue number	1
DOIs	https://doi.org/10.1038/s41467-017-01941-2
State	Published - 1 Dec 2017

Bibliographical note

Funding Information:
JMS is grateful for helpful discussions with Rachel Crespo-Otero regarding the molecular quantum-chemical calculations. This work was primarily supported by a UK Engineering and Physical Sciences Research Council (EPSRC) Programme Grant (grant no. EP/ K004956/1). The project also benefited from support from EPSRC grant no. EP/I01974X. SF is grateful for the support of a fellowship from the European Commission, under the Marie Curie Intra-European Fellowship scheme (PIEF-GA-2009-252883; SFL-PRR). The computational modelling was primarily carried out on the Archer high-performance computing facility, accessed through membership of the UK Materials Chemistry Consortium, which is funded by EPSRC grant no. EP/L000202. We also made use of the SiSu supercomputer at the IT Center for Science (CSC), Finland, via the Partnership for Advanced Computing in Europe (PRACE) project no. 13DECI0317/IsoSwitch. Some calculations were also performed on the Balena facility at the University of Bath, which is maintained by Bath University Computing Services. The Advanced Light Source is supported by the Director, Office of Science, Office of Basic Energy Sciences, of the US Department of Energy under Contract No. DE-AC02-05CH11231. We also thank Dr Robin Owen for the use of the spectrometer on Beamline I24 of the Diamond Light Source facility.

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© 2017 The Author(s).

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Bryant, M. J., Skelton, J. M., Hatcher, L. E., Stubbs, C., Madrid, E., Pallipurath, A. R., Thomas, L. H., Woodall, C. H., Christensen, J., Fuertes, S., Robinson, T. P., Beavers, C. M., Teat, S. J., Warren, M. R., Pradaux-Caggiano, F., Walsh, A., Marken, F., Carbery, D. R., Parker, S. C., ... Raithby, P. R. (2017). A rapidly-reversible absorptive and emissive vapochromic Pt(II) pincer-based chemical sensor. Nature Communications, 8(1), Article 1800. https://doi.org/10.1038/s41467-017-01941-2

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title = "A rapidly-reversible absorptive and emissive vapochromic Pt(II) pincer-based chemical sensor",

abstract = "Selective, robust and cost-effective chemical sensors for detecting small volatile-organic compounds (VOCs) have widespread applications in industry, healthcare and environmental monitoring. Here we design a Pt(II) pincer-Type material with selective absorptive and emissive responses to methanol and water. The yellow anhydrous form converts reversibly on a subsecond timescale to a red hydrate in the presence of parts-per-Thousand levels of atmospheric water vapour. Exposure to methanol induces a similarly-rapid and reversible colour change to a blue methanol solvate. Stable smart coatings on glass demonstrate robust switching over 104 cycles, and flexible microporous polymer membranes incorporating microcrystals of the complex show identical vapochromic behaviour. The rapid vapochromic response can be rationalised from the crystal structure, and in combination with quantum-chemical modelling, we provide a complete microscopic picture of the switching mechanism. We discuss how this multiscale design approach can be used to obtain new compounds with tailored VOC selectivity and spectral responses.",

author = "Bryant, {M. J.} and Skelton, {J. M.} and Hatcher, {L. E.} and C. Stubbs and E. Madrid and Pallipurath, {A. R.} and Thomas, {L. H.} and Woodall, {C. H.} and J. Christensen and S. Fuertes and Robinson, {T. P.} and Beavers, {C. M.} and Teat, {S. J.} and Warren, {M. R.} and F. Pradaux-Caggiano and A. Walsh and F. Marken and Carbery, {D. R.} and Parker, {S. C.} and McKeown, {N. B.} and R. Malpass-Evans and M. Carta and Raithby, {P. R.}",

note = "Funding Information: JMS is grateful for helpful discussions with Rachel Crespo-Otero regarding the molecular quantum-chemical calculations. This work was primarily supported by a UK Engineering and Physical Sciences Research Council (EPSRC) Programme Grant (grant no. EP/ K004956/1). The project also benefited from support from EPSRC grant no. EP/I01974X. SF is grateful for the support of a fellowship from the European Commission, under the Marie Curie Intra-European Fellowship scheme (PIEF-GA-2009-252883; SFL-PRR). The computational modelling was primarily carried out on the Archer high-performance computing facility, accessed through membership of the UK Materials Chemistry Consortium, which is funded by EPSRC grant no. EP/L000202. We also made use of the SiSu supercomputer at the IT Center for Science (CSC), Finland, via the Partnership for Advanced Computing in Europe (PRACE) project no. 13DECI0317/IsoSwitch. Some calculations were also performed on the Balena facility at the University of Bath, which is maintained by Bath University Computing Services. The Advanced Light Source is supported by the Director, Office of Science, Office of Basic Energy Sciences, of the US Department of Energy under Contract No. DE-AC02-05CH11231. We also thank Dr Robin Owen for the use of the spectrometer on Beamline I24 of the Diamond Light Source facility. Publisher Copyright: {\textcopyright} 2017 The Author(s).",

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Bryant, MJ, Skelton, JM, Hatcher, LE, Stubbs, C, Madrid, E, Pallipurath, AR, Thomas, LH, Woodall, CH, Christensen, J, Fuertes, S, Robinson, TP, Beavers, CM, Teat, SJ, Warren, MR, Pradaux-Caggiano, F, Walsh, A, Marken, F, Carbery, DR, Parker, SC, McKeown, NB, Malpass-Evans, R, Carta, M & Raithby, PR 2017, 'A rapidly-reversible absorptive and emissive vapochromic Pt(II) pincer-based chemical sensor', Nature Communications, vol. 8, no. 1, 1800. https://doi.org/10.1038/s41467-017-01941-2

TY - JOUR

T1 - A rapidly-reversible absorptive and emissive vapochromic Pt(II) pincer-based chemical sensor

AU - Bryant, M. J.

AU - Skelton, J. M.

AU - Hatcher, L. E.

AU - Stubbs, C.

AU - Madrid, E.

AU - Pallipurath, A. R.

AU - Thomas, L. H.

AU - Woodall, C. H.

AU - Christensen, J.

AU - Fuertes, S.

AU - Robinson, T. P.

AU - Beavers, C. M.

AU - Teat, S. J.

AU - Warren, M. R.

AU - Pradaux-Caggiano, F.

AU - Walsh, A.

AU - Marken, F.

AU - Carbery, D. R.

AU - Parker, S. C.

AU - McKeown, N. B.

AU - Malpass-Evans, R.

AU - Carta, M.

AU - Raithby, P. R.

N1 - Funding Information: JMS is grateful for helpful discussions with Rachel Crespo-Otero regarding the molecular quantum-chemical calculations. This work was primarily supported by a UK Engineering and Physical Sciences Research Council (EPSRC) Programme Grant (grant no. EP/ K004956/1). The project also benefited from support from EPSRC grant no. EP/I01974X. SF is grateful for the support of a fellowship from the European Commission, under the Marie Curie Intra-European Fellowship scheme (PIEF-GA-2009-252883; SFL-PRR). The computational modelling was primarily carried out on the Archer high-performance computing facility, accessed through membership of the UK Materials Chemistry Consortium, which is funded by EPSRC grant no. EP/L000202. We also made use of the SiSu supercomputer at the IT Center for Science (CSC), Finland, via the Partnership for Advanced Computing in Europe (PRACE) project no. 13DECI0317/IsoSwitch. Some calculations were also performed on the Balena facility at the University of Bath, which is maintained by Bath University Computing Services. The Advanced Light Source is supported by the Director, Office of Science, Office of Basic Energy Sciences, of the US Department of Energy under Contract No. DE-AC02-05CH11231. We also thank Dr Robin Owen for the use of the spectrometer on Beamline I24 of the Diamond Light Source facility. Publisher Copyright: © 2017 The Author(s).

PY - 2017/12/1

Y1 - 2017/12/1

N2 - Selective, robust and cost-effective chemical sensors for detecting small volatile-organic compounds (VOCs) have widespread applications in industry, healthcare and environmental monitoring. Here we design a Pt(II) pincer-Type material with selective absorptive and emissive responses to methanol and water. The yellow anhydrous form converts reversibly on a subsecond timescale to a red hydrate in the presence of parts-per-Thousand levels of atmospheric water vapour. Exposure to methanol induces a similarly-rapid and reversible colour change to a blue methanol solvate. Stable smart coatings on glass demonstrate robust switching over 104 cycles, and flexible microporous polymer membranes incorporating microcrystals of the complex show identical vapochromic behaviour. The rapid vapochromic response can be rationalised from the crystal structure, and in combination with quantum-chemical modelling, we provide a complete microscopic picture of the switching mechanism. We discuss how this multiscale design approach can be used to obtain new compounds with tailored VOC selectivity and spectral responses.

AB - Selective, robust and cost-effective chemical sensors for detecting small volatile-organic compounds (VOCs) have widespread applications in industry, healthcare and environmental monitoring. Here we design a Pt(II) pincer-Type material with selective absorptive and emissive responses to methanol and water. The yellow anhydrous form converts reversibly on a subsecond timescale to a red hydrate in the presence of parts-per-Thousand levels of atmospheric water vapour. Exposure to methanol induces a similarly-rapid and reversible colour change to a blue methanol solvate. Stable smart coatings on glass demonstrate robust switching over 104 cycles, and flexible microporous polymer membranes incorporating microcrystals of the complex show identical vapochromic behaviour. The rapid vapochromic response can be rationalised from the crystal structure, and in combination with quantum-chemical modelling, we provide a complete microscopic picture of the switching mechanism. We discuss how this multiscale design approach can be used to obtain new compounds with tailored VOC selectivity and spectral responses.

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DO - 10.1038/s41467-017-01941-2

M3 - Article

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AN - SCOPUS:85035316014

SN - 2041-1723

VL - 8

JO - Nature Communications

JF - Nature Communications

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ER -

A rapidly-reversible absorptive and emissive vapochromic Pt(II) pincer-based chemical sensor

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