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

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 10 4 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.
Authors:
ORCiD logo [1] ;  [2] ;  [3] ;  [2] ;  [2] ; ORCiD logo [2] ;  [2] ;  [2] ;  [4] ; ORCiD logo [2] ;  [2] ; ORCiD logo [5] ; ORCiD logo [5] ;  [6] ;  [2] ; ORCiD logo [7] ;  [2] ;  [2] ; ORCiD logo [2] ;  [8] more »;  [8] ; ORCiD logo [8] ; ORCiD logo [3] « less
  1. Univ. of Bath, Bath (United Kingdom); The Cambridge Crystallographic Data Centre, Cambridge (United Kingdom)
  2. Univ. of Bath, Bath (United Kingdom)
  3. Univ. of Bath, Bath (United Kingdom); Rutherford Appleton Lab., Oxfordshire (United Kingdom)
  4. Rutherford Appleton Lab., Oxfordshire (United Kingdom)
  5. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  6. Diamond Light Source, Oxfordshire (United Kingdom)
  7. Univ. of Bath, Bath (United Kingdom); Yonsei Univ., Seoul (Korea)
  8. Univ. of Edinburgh, Edinburgh (United Kingdom)
Publication Date:
Grant/Contract Number:
AC02-05CH11231
Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 8; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Research Org:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1417623

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., McKeown, N. B., Malpass-Evans, R., Carta, M., and Raithby, P. R.. A rapidly-reversible absorptive and emissive vapochromic Pt(II) pincer-based chemical sensor. United States: N. p., Web. doi:10.1038/s41467-017-01941-2.
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., McKeown, N. B., Malpass-Evans, R., Carta, M., & Raithby, P. R.. A rapidly-reversible absorptive and emissive vapochromic Pt(II) pincer-based chemical sensor. United States. doi:10.1038/s41467-017-01941-2.
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., McKeown, N. B., Malpass-Evans, R., Carta, M., and Raithby, P. R.. 2017. "A rapidly-reversible absorptive and emissive vapochromic Pt(II) pincer-based chemical sensor". United States. doi:10.1038/s41467-017-01941-2. https://www.osti.gov/servlets/purl/1417623.
@article{osti_1417623,
title = {A rapidly-reversible absorptive and emissive vapochromic Pt(II) pincer-based chemical sensor},
author = {Bryant, M. J. and Skelton, J. M. and Hatcher, L. E. and Stubbs, C. and Madrid, E. and Pallipurath, A. R. and Thomas, L. H. and Woodall, C. H. and Christensen, J. and Fuertes, S. and Robinson, T. P. and Beavers, C. M. and Teat, S. J. and Warren, M. R. and Pradaux-Caggiano, F. and Walsh, A. and Marken, F. and Carbery, D. R. and Parker, S. C. and McKeown, N. B. and Malpass-Evans, R. and Carta, M. and Raithby, P. R.},
abstractNote = {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.},
doi = {10.1038/s41467-017-01941-2},
journal = {Nature Communications},
number = 1,
volume = 8,
place = {United States},
year = {2017},
month = {11}
}

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