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A novel fluorescence “on–off–on” chemosensor for Hg²⁺ via a water-assistant blocking heavy atom effect

Wu, Chong; Zhao, Jiang-Lin; Jiang, Xue-Kai; Wang, Chuan-Zeng; Ni, Xin-Long; Zeng, Xi; Redshaw, Carl; Yamato, Takehiko


Chong Wu

Jiang-Lin Zhao

Xue-Kai Jiang

Chuan-Zeng Wang

Xin-Long Ni

Xi Zeng

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Professor Carl Redshaw
Professor of Inorganic Materials Chemistry and REF Lead for Chemistry

Takehiko Yamato


Upper rim pyrene-functionalized hexahomotrioxacalix[3]arene L was synthesized via Click chemistry, and its fluorescence behaviors toward several common metal cations were investigated. L exhibited a significant fluorescence quenching response to Hg²⁺ in CH₃CN solution, which was unaffected by the coexistence of other competitive metal cations. Thus, L can be utilized as a highly selective and sensitive fluorescent chemosensor for Hg²⁺ with a detection limit in the nM level. Interestingly, the quenched fluorescence emission can be successfully revived upon the addition of water. In this process, the heavy atom effect of Hg²⁺ can be blocked by further coordination of a water molecule and resulted in the revival of the fluorescence emission of L/Hg²⁺ complex. Particularly, other polar solvents such as CH₃OH and CH₃CH₂OH also have the ability to revive the fluorescence emission of the L/Hg²⁺ complex, but on a much smaller scale than observed for H₂O. The heavy atom effect and blocking thereof were demonstrated within the same system by the use of a C₃-symmetric homooxacalix[3]arene scaffold. The present studies provided further evidence for the blocking heavy atom effect.


Wu, C., Zhao, J., Jiang, X., Wang, C., Ni, X., Zeng, X., …Yamato, T. (2016). A novel fluorescence “on–off–on” chemosensor for Hg²⁺ via a water-assistant blocking heavy atom effect. Dalton Transactions : an international journal of inorganic chemistry, 45(38), 14948-14953.

Acceptance Date Aug 16, 2016
Online Publication Date Aug 17, 2016
Publication Date Aug 17, 2016
Deposit Date Aug 23, 2016
Publicly Available Date Aug 23, 2016
Journal Dalton transactions
Print ISSN 1477-9226
Electronic ISSN 1477-9234
Publisher Royal Society of Chemistry
Peer Reviewed Peer Reviewed
Volume 45
Issue 38
Pages 14948-14953
Keywords Fluorescence, Heavy atom effect, Chemosensor, L/Hg²⁺ complex
Public URL
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Additional Information : This document is Similarity Check deposited; : Supplementary Information; : The Royal Society of Chemistry has an exclusive publication licence for this journal; : Single-blind; : Received 8 June 2016; Accepted 16 August 2016; Accepted Manuscript published 17 August 2016; Advance Article published 23 August 2016; Version of Record published 27 September 2016


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