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

被引:89
作者
Bryant, M. J. [1 ,2 ]
Skelton, J. M. [1 ]
Hatcher, L. E. [1 ,3 ]
Stubbs, C. [1 ]
Madrid, E. [1 ]
Pallipurath, A. R. [1 ]
Thomas, L. H. [1 ]
Woodall, C. H. [1 ]
Christensen, J. [3 ]
Fuertes, S. [1 ]
Robinson, T. P. [1 ]
Beavers, C. M. [4 ]
Teat, S. J. [4 ]
Warren, M. R. [5 ]
Pradaux-Caggiano, F. [1 ]
Walsh, A. [1 ,6 ,7 ]
Marken, F. [1 ]
Carbery, D. R. [1 ]
Parker, S. C. [1 ]
McKeown, N. B. [8 ]
Malpass-Evans, R. [8 ]
Carta, M. [8 ]
Raithby, P. R. [1 ,3 ]
机构
[1] Univ Bath, Dept Chem, Bath BA2 7AY, Avon, England
[2] Cambridge Crystallog Data Ctr, 12 Union Rd, Cambridge CB2 1EZ, England
[3] Rutherford Appleton Lab, Res Complex Harwell, Didcot OX11 0FA, Oxon, England
[4] Lawrence Berkeley Natl Lab, Adv Light Source, 1 Cyclotron Rd, Berkeley, CA 94720 USA
[5] Diamond Light Source, Beamline I19, Harwell Sci & Innovat Campus, Didcot OX11 0QX, Oxon, England
[6] Yonsei Univ, Global Inst E3, Seoul 120749, South Korea
[7] Yonsei Univ, Dept Mat Sci & Engn, Seoul 120749, South Korea
[8] Univ Edinburgh, EastChem, Sch Chem, Edinburgh EH9 3FJ, Midlothian, Scotland
基金
英国工程与自然科学研究理事会;
关键词
CYCLOMETALATED PLATINUM(II) COMPLEXES; PI-PI INTERACTIONS; CENTER-DOT-PT; SPECTROSCOPIC PROPERTIES; PHOTOPHYSICAL PROPERTIES; RED FORM; LIGANDS; ENERGY;
D O I
10.1038/s41467-017-01941-2
中图分类号
O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];
学科分类号
07 ; 0710 ; 09 ;
摘要
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.
引用
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页数:9
相关论文
共 55 条
[1]   A search for the elusive red form in substituted Pt-II bipyridine complexes [J].
Achar, S ;
Catalano, VJ .
POLYHEDRON, 1997, 16 (09) :1555-1561
[2]   Toward reliable density functional methods without adjustable parameters: The PBE0 model [J].
Adamo, C ;
Barone, V .
JOURNAL OF CHEMICAL PHYSICS, 1999, 110 (13) :6158-6170
[3]   Organoplatinum crystals for gas-triggered switches [J].
Albrecht, M ;
Lutz, M ;
Spek, AL ;
van Koten, G .
NATURE, 2000, 406 (6799) :970-974
[4]  
Aliprandi A, 2016, NAT CHEM, V8, P10, DOI [10.1038/NCHEM.2383, 10.1038/nchem.2383]
[5]  
[Anonymous], J BREATH RES
[6]  
[Anonymous], J CHEM PHYS
[7]  
[Anonymous], J CHEM PHYS
[8]  
[Anonymous], ORGANOMETALLICS
[9]   Organometallic benzylidene anilines: donor-acceptor features in NCN-pincer Pt(II) complexes with a 4-(E)-[(4-R-phenyl)imino]methyl substituent [J].
Batema, Guido D. ;
Lutz, Martin ;
Spek, Anthony L. ;
van Walree, Cornelis A. ;
van Klink, Gerard P. M. ;
van Koten, Gerard .
DALTON TRANSACTIONS, 2014, 43 (32) :12200-12209
[10]   Synthesis, characterization and photophysics of a new series of anionic C,N,C cyclometalated platinum complexes [J].
Berenguer, Jesus R. ;
Lalinde, Elena ;
Torroba, Javier .
INORGANIC CHEMISTRY, 2007, 46 (23) :9919-9930