Fluorescent in based MOFs showing "turn on" luminescence towards thiols and acting as a ratiometric fluorescence thermometer

Zhao Feng Wu, Bin Tan, Ever Velasco, Hao Wang, Nan Nan Shen, Yu Jie Gao, Xu Zhang, Kun Zhu, Guo Yu Zhang, Yan Yao Liu, Xiu Ze Hei, Xiao Ying Huang, Jing Li

Research output: Contribution to journalArticle

Abstract

Herein, two indium-based metal organic frameworks (In-MOFs), namely [(CH 3 ) 2 NH 2 ][In(bpdc) 2 ]·(DMF) 2 (1) and [(CH 3 ) 2 NH 2 ] 3 [(In 3 Cl 2 )(bpdc) 5 ]·(H 2 O) 5 (DMF) 2.5 (2, bpdcH 2 = 4,4′-biphenyldicarboxylic acid), have been synthesized and characterized. By introducing a Cl - ion as a terminal ligand to break the symmetrical coordination environment of a typical InO 8 dodecahedron as that in a three dimensional (3D) compound 1 with a 4-connected and four-fold interpenetrating dia net topology, a chiral 2D compound 2 with unique double-helical chains along the c axis is generated. Fluorescence (FL) measurements indicate that both compounds demonstrate excellent FL sensing behaviour towards CS 2 , a trace amount of Fe 3+ ions and nitro-containing explosives. Notably, the layered 2 exhibits a unique "turn on" FL sensing behaviour towards thiol molecules, e.g., cysteine and 1-butylmercaptan, by exfoliating 2 into a few-layer FL material. The detection mechanism was investigated in detail by multiple characterizations including but not limited to EDS, SEM and AFM. The [(CH 3 ) 2 NH 2 ] + cations in 2 can be replaced by an Eu 3+ ion to generate 2@Eu 3+ which exhibits a new characteristic sharp red emission of Eu 3+ . More importantly, 2@Eu 3+ can serve as a convenient ratiometric FL sensor for temperature, demonstrating obvious color changes from weak purple to red under UV light as the temperature increases. Furthermore, cationic green- and red-light emitting dyes incorporated with 2@dyes emit white light with 17.28% quantum yield.

Original languageEnglish
Pages (from-to)3049-3055
Number of pages7
JournalJournal of Materials Chemistry C
Volume7
Issue number10
DOIs
Publication statusPublished - Jan 1 2019

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Thermometers
Sulfhydryl Compounds
Luminescence
Fluorescence
Ions
Dyes
Indium
Quantum yield
Ultraviolet radiation
Cysteine
Cations
Energy dispersive spectroscopy
Coloring Agents
Positive ions
Metals
Ligands
Topology
Color
Temperature
Scanning electron microscopy

ASJC Scopus subject areas

  • Chemistry(all)
  • Materials Chemistry

Cite this

Fluorescent in based MOFs showing "turn on" luminescence towards thiols and acting as a ratiometric fluorescence thermometer. / Wu, Zhao Feng; Tan, Bin; Velasco, Ever; Wang, Hao; Shen, Nan Nan; Gao, Yu Jie; Zhang, Xu; Zhu, Kun; Zhang, Guo Yu; Liu, Yan Yao; Hei, Xiu Ze; Huang, Xiao Ying; Li, Jing.

In: Journal of Materials Chemistry C, Vol. 7, No. 10, 01.01.2019, p. 3049-3055.

Research output: Contribution to journalArticle

Wu, ZF, Tan, B, Velasco, E, Wang, H, Shen, NN, Gao, YJ, Zhang, X, Zhu, K, Zhang, GY, Liu, YY, Hei, XZ, Huang, XY & Li, J 2019, 'Fluorescent in based MOFs showing "turn on" luminescence towards thiols and acting as a ratiometric fluorescence thermometer', Journal of Materials Chemistry C, vol. 7, no. 10, pp. 3049-3055. https://doi.org/10.1039/c9tc00463g
Wu, Zhao Feng ; Tan, Bin ; Velasco, Ever ; Wang, Hao ; Shen, Nan Nan ; Gao, Yu Jie ; Zhang, Xu ; Zhu, Kun ; Zhang, Guo Yu ; Liu, Yan Yao ; Hei, Xiu Ze ; Huang, Xiao Ying ; Li, Jing. / Fluorescent in based MOFs showing "turn on" luminescence towards thiols and acting as a ratiometric fluorescence thermometer. In: Journal of Materials Chemistry C. 2019 ; Vol. 7, No. 10. pp. 3049-3055.
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abstract = "Herein, two indium-based metal organic frameworks (In-MOFs), namely [(CH 3 ) 2 NH 2 ][In(bpdc) 2 ]·(DMF) 2 (1) and [(CH 3 ) 2 NH 2 ] 3 [(In 3 Cl 2 )(bpdc) 5 ]·(H 2 O) 5 (DMF) 2.5 (2, bpdcH 2 = 4,4′-biphenyldicarboxylic acid), have been synthesized and characterized. By introducing a Cl - ion as a terminal ligand to break the symmetrical coordination environment of a typical InO 8 dodecahedron as that in a three dimensional (3D) compound 1 with a 4-connected and four-fold interpenetrating dia net topology, a chiral 2D compound 2 with unique double-helical chains along the c axis is generated. Fluorescence (FL) measurements indicate that both compounds demonstrate excellent FL sensing behaviour towards CS 2 , a trace amount of Fe 3+ ions and nitro-containing explosives. Notably, the layered 2 exhibits a unique {"}turn on{"} FL sensing behaviour towards thiol molecules, e.g., cysteine and 1-butylmercaptan, by exfoliating 2 into a few-layer FL material. The detection mechanism was investigated in detail by multiple characterizations including but not limited to EDS, SEM and AFM. The [(CH 3 ) 2 NH 2 ] + cations in 2 can be replaced by an Eu 3+ ion to generate 2@Eu 3+ which exhibits a new characteristic sharp red emission of Eu 3+ . More importantly, 2@Eu 3+ can serve as a convenient ratiometric FL sensor for temperature, demonstrating obvious color changes from weak purple to red under UV light as the temperature increases. Furthermore, cationic green- and red-light emitting dyes incorporated with 2@dyes emit white light with 17.28{\%} quantum yield.",
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AU - Wu, Zhao Feng

AU - Tan, Bin

AU - Velasco, Ever

AU - Wang, Hao

AU - Shen, Nan Nan

AU - Gao, Yu Jie

AU - Zhang, Xu

AU - Zhu, Kun

AU - Zhang, Guo Yu

AU - Liu, Yan Yao

AU - Hei, Xiu Ze

AU - Huang, Xiao Ying

AU - Li, Jing

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N2 - Herein, two indium-based metal organic frameworks (In-MOFs), namely [(CH 3 ) 2 NH 2 ][In(bpdc) 2 ]·(DMF) 2 (1) and [(CH 3 ) 2 NH 2 ] 3 [(In 3 Cl 2 )(bpdc) 5 ]·(H 2 O) 5 (DMF) 2.5 (2, bpdcH 2 = 4,4′-biphenyldicarboxylic acid), have been synthesized and characterized. By introducing a Cl - ion as a terminal ligand to break the symmetrical coordination environment of a typical InO 8 dodecahedron as that in a three dimensional (3D) compound 1 with a 4-connected and four-fold interpenetrating dia net topology, a chiral 2D compound 2 with unique double-helical chains along the c axis is generated. Fluorescence (FL) measurements indicate that both compounds demonstrate excellent FL sensing behaviour towards CS 2 , a trace amount of Fe 3+ ions and nitro-containing explosives. Notably, the layered 2 exhibits a unique "turn on" FL sensing behaviour towards thiol molecules, e.g., cysteine and 1-butylmercaptan, by exfoliating 2 into a few-layer FL material. The detection mechanism was investigated in detail by multiple characterizations including but not limited to EDS, SEM and AFM. The [(CH 3 ) 2 NH 2 ] + cations in 2 can be replaced by an Eu 3+ ion to generate 2@Eu 3+ which exhibits a new characteristic sharp red emission of Eu 3+ . More importantly, 2@Eu 3+ can serve as a convenient ratiometric FL sensor for temperature, demonstrating obvious color changes from weak purple to red under UV light as the temperature increases. Furthermore, cationic green- and red-light emitting dyes incorporated with 2@dyes emit white light with 17.28% quantum yield.

AB - Herein, two indium-based metal organic frameworks (In-MOFs), namely [(CH 3 ) 2 NH 2 ][In(bpdc) 2 ]·(DMF) 2 (1) and [(CH 3 ) 2 NH 2 ] 3 [(In 3 Cl 2 )(bpdc) 5 ]·(H 2 O) 5 (DMF) 2.5 (2, bpdcH 2 = 4,4′-biphenyldicarboxylic acid), have been synthesized and characterized. By introducing a Cl - ion as a terminal ligand to break the symmetrical coordination environment of a typical InO 8 dodecahedron as that in a three dimensional (3D) compound 1 with a 4-connected and four-fold interpenetrating dia net topology, a chiral 2D compound 2 with unique double-helical chains along the c axis is generated. Fluorescence (FL) measurements indicate that both compounds demonstrate excellent FL sensing behaviour towards CS 2 , a trace amount of Fe 3+ ions and nitro-containing explosives. Notably, the layered 2 exhibits a unique "turn on" FL sensing behaviour towards thiol molecules, e.g., cysteine and 1-butylmercaptan, by exfoliating 2 into a few-layer FL material. The detection mechanism was investigated in detail by multiple characterizations including but not limited to EDS, SEM and AFM. The [(CH 3 ) 2 NH 2 ] + cations in 2 can be replaced by an Eu 3+ ion to generate 2@Eu 3+ which exhibits a new characteristic sharp red emission of Eu 3+ . More importantly, 2@Eu 3+ can serve as a convenient ratiometric FL sensor for temperature, demonstrating obvious color changes from weak purple to red under UV light as the temperature increases. Furthermore, cationic green- and red-light emitting dyes incorporated with 2@dyes emit white light with 17.28% quantum yield.

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