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Resonant plasmon‐enhanced absorption of charge transfer complexes in a metal–organic monolayer

Resonant plasmon‐enhanced absorption of charge transfer complexes in a metal–organic monolayer
Resonant plasmon‐enhanced absorption of charge transfer complexes in a metal–organic monolayer
Plasmonic enhancement of absorption in charge‐transfer (CT) complexes formed under NO2 gas adsorption onto 2D hybrid structure, based on the metal–organic monolayer and gold nanoparticles (AuNPs), is demonstrated. By using Langmuir–Blodgett deposition of low‐symmetry zinc phthalocyanine (ZnPc) molecules, the metal–organic monolayer is fabricated with greatly suppressed intermolecular aggregation. Oxidation of the monolayer through coordination of NO2 molecules with axial zinc ions of ZnPc molecules gives rise to the specific absorption band inherited to cation radical ZnPc+. The hybrid AuNPs–ZnPc structure is engineered to maximize exciton–plasmon interaction of CT complexes at the radical form of the metal–organic monolayer. Excellent spectral and spatial overlaps with plasmon resonance boost absorption of CT internal optical transition, so‐called “fingerprint” band, by a factor of six from 0.45% to 2.8% in total. The approach paves the way for efficient plasmonic control over photochemical reactions promoted by charge‐transfer complexes in metal–organic films. In particular, the plasmonic effect is harnessed to improve NO2 gas sensing properties; the experimental study shows a 15‐fold increase of the detection efficiency in the specific band of CT complexes under the gas exposure.
charge‐transfer complexes, gas sensor, hybrid monolayers, resonant plasmon enhancement
2195-1071
Zasedatelev, Anton
b8f8265a-58a1-48c8-abf5-68e4e6ef8f70
Krichevsky, Denis
a52d13cf-dddb-45d6-b659-e88089c950c1
Tolbin, Alexander
39a2bdee-7e7b-4f51-b171-61609c31d723
Dubinina, Tatiana
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Kosolobov, Sergey
61560580-d8d8-4b76-8588-8bb10bd1aead
Krasovskii, Vitally
85fd1ed4-29db-4690-8bec-c5e0bc5255c8
Tomilova, Larisa
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Pushkarev, Victor
716238e5-01eb-434f-adde-34a75c752f7b
Zasedatelev, Anton
b8f8265a-58a1-48c8-abf5-68e4e6ef8f70
Krichevsky, Denis
a52d13cf-dddb-45d6-b659-e88089c950c1
Tolbin, Alexander
39a2bdee-7e7b-4f51-b171-61609c31d723
Dubinina, Tatiana
a31ac076-6c3b-453b-a6c0-4ffc84d703ca
Kosolobov, Sergey
61560580-d8d8-4b76-8588-8bb10bd1aead
Krasovskii, Vitally
85fd1ed4-29db-4690-8bec-c5e0bc5255c8
Tomilova, Larisa
10b1297c-0d4c-43a9-a35c-3d920798e831
Pushkarev, Victor
716238e5-01eb-434f-adde-34a75c752f7b

Zasedatelev, Anton, Krichevsky, Denis, Tolbin, Alexander, Dubinina, Tatiana, Kosolobov, Sergey, Krasovskii, Vitally, Tomilova, Larisa and Pushkarev, Victor (2021) Resonant plasmon‐enhanced absorption of charge transfer complexes in a metal–organic monolayer. Advanced Optical Materials, 9 (11), [2100065]. (doi:10.1002/adom.202100065).

Record type: Article

Abstract

Plasmonic enhancement of absorption in charge‐transfer (CT) complexes formed under NO2 gas adsorption onto 2D hybrid structure, based on the metal–organic monolayer and gold nanoparticles (AuNPs), is demonstrated. By using Langmuir–Blodgett deposition of low‐symmetry zinc phthalocyanine (ZnPc) molecules, the metal–organic monolayer is fabricated with greatly suppressed intermolecular aggregation. Oxidation of the monolayer through coordination of NO2 molecules with axial zinc ions of ZnPc molecules gives rise to the specific absorption band inherited to cation radical ZnPc+. The hybrid AuNPs–ZnPc structure is engineered to maximize exciton–plasmon interaction of CT complexes at the radical form of the metal–organic monolayer. Excellent spectral and spatial overlaps with plasmon resonance boost absorption of CT internal optical transition, so‐called “fingerprint” band, by a factor of six from 0.45% to 2.8% in total. The approach paves the way for efficient plasmonic control over photochemical reactions promoted by charge‐transfer complexes in metal–organic films. In particular, the plasmonic effect is harnessed to improve NO2 gas sensing properties; the experimental study shows a 15‐fold increase of the detection efficiency in the specific band of CT complexes under the gas exposure.

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e-pub ahead of print date: 17 March 2021
Published date: 2021
Additional Information: Funding Information: D.M.K. thanks D.O. Ignatyeva and A.N. Kalish for fruitful discussions on plasmon‐assisted optical phenomena. The work was supported by the Russian Science Foundation (Grant No. 20‐72‐10145). A.Y.T. acknowledges the support by the State Assignment of 2020 (Theme 45.5 Creation of compounds with given physicochemical properties, No 0090‐2019‐0003) concerning the synthesis and quantum‐chemical investigations of the phthalocyanine. V.E.P. acknowledges support by Council under the President of the Russian Federation for State Support of Young Scientists and Leading Scientific Schools (Grant MD‐3847.2019.3). Authors thank the Joint Supercomputer Centre of RAS ( www.jscc.ru ) for providing computing resources. Publisher Copyright: © 2021 The Authors. Advanced Optical Materials published by Wiley-VCH GmbH Copyright: Copyright 2021 Elsevier B.V., All rights reserved.
Keywords: charge‐transfer complexes, gas sensor, hybrid monolayers, resonant plasmon enhancement

Identifiers

Local EPrints ID: 448490
URI: http://eprints.soton.ac.uk/id/eprint/448490
ISSN: 2195-1071
PURE UUID: 98807c72-4079-42e6-87de-21adc0aaf8cb
ORCID for Anton Zasedatelev: ORCID iD orcid.org/0000-0003-0414-5779

Catalogue record

Date deposited: 23 Apr 2021 16:31
Last modified: 26 Nov 2021 03:18

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Contributors

Author: Denis Krichevsky
Author: Alexander Tolbin
Author: Tatiana Dubinina
Author: Sergey Kosolobov
Author: Vitally Krasovskii
Author: Larisa Tomilova
Author: Victor Pushkarev

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