- Email: [email protected]
Functionalization of epindolidion: a new colorimetric and ratiometric fluorescent probe for Hg2+
Accepted Manuscript Functionalization of Epindolidion: A New Colorimetric and Ratiometric Fluorescent Probe for Hg2+ Yue Wu, Xiaofei Cai, Shengying Wu, Limin Wang, Guifeng Wang, Feng Wang PII: DOI: Reference:
S0040-4039(16)30745-6 http://dx.doi.org/10.1016/j.tetlet.2016.06.075 TETL 47802
To appear in:
Tetrahedron Letters
Received Date: Revised Date: Accepted Date:
12 April 2016 13 June 2016 17 June 2016
Please cite this article as: Wu, Y., Cai, X., Wu, S., Wang, L., Wang, G., Wang, F., Functionalization of Epindolidion: A New Colorimetric and Ratiometric Fluorescent Probe for Hg2+, Tetrahedron Letters (2016), doi: http://dx.doi.org/ 10.1016/j.tetlet.2016.06.075
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
1
Tetrahedron Letters j ou r n a l h o m ep a g e : w w w . e ls e vi e r . c o m
Functionalization of Epindolidion: a New Colorimetric and Ratiometric Fluorescent Probe for Hg2+ Yue Wua, #, Xiaofei Caia, #, Shengying Wua, , Limin Wanga, , Guifeng Wang b and Feng Wangb a
Shanghai Key Laboratory of Functional Materials Chemistry, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, China Lily Group CO. LTD, Nong Yi Chang Town, Linjiang Industrial Park, Xiaoshan Dis., Hangzhou City, Zhejiang Province 311228, China # These authors contributed equally to this work b
A RT I C L E I N F O
A BS T RA C T
Article history: Received Received in revised form Accepted Available online
After functionalization, a new epindolidion derivative bearing a vinyl group was synthesized as a naked-eye fluorescent probe for Hg 2+ through two steps. The probe showed good selectivity to Hg2+ over other metal cations in CH 3CN. On the basis of the addition of Hg2+, the fluorescence emission of the probe at 485 nm was ratio quenched along with the appearance of the new peak at 574 nm. Simultaneously, the absorbance of the probe showed bathochromic shift as a function of the increasing concentration of Hg2+. All of the features mentioned make this compound a useful probe for Hg2+ measurement. To the best of our knowledge, it’s the first fluorescent probe based on epindolidion.
Keywords: Epindolidion derivative Mercury ion Colorimetric Ratiometric fluorescent Probe
1. Introduction Many kinds of dyes and pigments have been functionalized into molecular devices and advanced materials, making “old dyes” into “new materials”1. For instance, derivatives of chromophores, such as naphthalimide, peryleneimide, coumarin, quinacridone and diketopyrrolopyrrole, were widely introduced into photovoltaic materials2-3, organic soft materials4, fluorescent chemosensors5-6 and other functional materials7-8. Epindolidion and its derivatives are a class of brilliant yellow pigments with strong fluorescence and show high performance, such as exceptional light, weather and heat stability for the intermolecular hydrogen bond7, 9-11. For a long time chemists have focused considerable and consistent attentions on their synthesis and pigment performance, and only a few researches were reported on functionalization of epindolidions, making them to be wonderful potential materials for organic semiconductors, Field-Effect Transistors and Light-Emitting Diodes12-14. Based on exploration about synthesis optimizing of epindolidions in our group15, it is meaningful to do more researches on the fluorescence features of epindolidions in solution to widen their applications. Following our interest on chemosensors of different chromophores16-19, a derivative of epindolidion with good solubility was designed as a “naked-eye” colorimetric and ratiometric fluorescent probe for mercury ions. As one of the most toxic heavy metal elements, mercury can lead to the
———
2009 Elsevier Ltd. All rights reserved .
dysfunction of the organism, so there is an increasing interest in the design and development of chemical probes for mercury ion20. Moreover, to the best of our knowledge, there are no reports on the fluorescent probes based on epindolidion derivatives. Herein, a new epindolidion derivative was designed and synthesized, with an allyl group contacted on the N atom as Hg2+ receptor based on mercuration reaction 21. The chemosensor 3 (Scheme 1) in this paper was found to be effectively colorimetric and ratiometric fluorescent probes for naked-eye detection of Hg2+.
Scheme 1 Synthetic routes of Epindolidion derivatives.
Corresponding author. Tel.: +86-021-6425-3881; fax: +86-021-6425-3881; e-mail: [email protected] Corresponding author. Tel.: +86-021-6425-3881; fax: +86-021-6425-3881; e-mail: [email protected]
2
Tetrahedron Letters 2. Results and discussion
2.1. Synthesis of compound 3 Compound 3 was synthesized by a two-step procedure from epindolidion (Scheme 1), and the final products were obtained after purified by silica gel chromatography (see details in ESI†). 2.2. Colorimetric and Ratiometric Fluorescent Probe of Fluoride Ions In order to obtain a naked-eye result, the probe was examined at the concentration of 5×10-5 M. The selectivity of the probe toward Hg2+ over other competitive species was investigated in the presence of various biologically and environmentally relevant metal ions. All the measurements were conducted by using the chloride metal ion in aqueous buffer. Among the various metal ions tested, the probe detected Hg 2+ while other relevant metals did not modulate the absorption and fluorescence spectrum (Figure 1 (a), (b)). Thus, the probe seemed to be useful for selectively sensing, even with these relevant analytes.
0.6
(a)
probe,probe+Pb2+,Zn2+,Cd2+,Ag+, Ni2+,Cu2+,Fe2+,Cr3+,Mn2+,Co2+,Ca2+, Mg2+,K+,Na+
Absorbance
0.5
Figure 2 The fluorescence emission response of the probe (5×10-5 M) on addition of 5×10-5 M cations in the form of chloride salts in aqueous solution of acetonitrile excited at 365 nm using UV lamp.( Left to right: probe, probe + Hg2+, Pb2+, Zn2+, Cd2+, Ag+, Ni2+, Cu2+, Fe2+, Cr3+, Mn2+, Co2+, Ca2+, Mg2+, K+, Na+.)
Figure 3 1H NMR spectra of “probe” and “probe+Hg2+” .
0.4
probe+Hg2+
0.3
0.2
0.1
Figure 4 The mass spectrometry analysis of the complexation probe-[HgCl]+.
0.0 400
450
500
550
600
Wavelength/nm
18000
(b)
16000
probe,probe+Pb2+,Zn2+,Cd2+,Ag+, Ni2+,Cu2+,Fe2+,Cr3+,Mn2+,Co2+,Ca2+, Mg2+,K+,Na+
Intensity/au
14000 12000
The molecular behavior was studied by 1H NMR and mass spectrometry. In the 1H NMR spectra of “probe+Hg2+”, signals of the aromatic protons dramatically changed, and signals of H1, H2 and H3 were found at d = 4.0-5.5 ppm (Figure 3). Both mass spectrometry analysis (m/z 707.2057) and the 1H NMR spectra indicated the formation of onium ions21 (Scheme 2, Figures 3-4).
10000 8000 6000 4000
probe+Hg2+
2000 0 500
Scheme 2 The proposed binding mode of compound 3 and Hg2+.
550
600
650
700
Wavelength/nm
Figure 1 UV-Vis (a) and fluorescence (b) spectra of the probe (5×10-5 M) in CH3CN in the presence of different metal ions at 25 oC, λex = 471 nm.
Notably, the red shift combined with large ratiometric absorbtion and fluorescent response rendered the probe suitable for detection of Hg2+ by simple visual inspection (Figure 2). However, the competition between Hg2+ and other metals showed no significant quenching in the sample. The reason might be that the redundant anions caused equilibrium shifted from more reactive [HgCl]+ to less reactive HgCl2.
Upon progressive addition of Hg2+, the maximum absorption wavelength of the probe at 460 nm was decreased gradually, meanwhile the new absorbance wavelength (511 nm) of the maximum could be observed and increased (Figure 5(a)). Also, from the clear isosbestic points at 471 nm, it indicated the formation of new compound. Excited at 471 nm, the free probe showed an intense emission at 485 nm, however, the addition of Hg2+ led to a drastic decrease at 485 nm and simultaneous appearance of a new emission band at 574 nm, as showed in the Figure 5(b). As a result, the probe performed as a colorimetric and ratiometric fluorescent probe (Figure 6(a), (b)). From the evidence above, the probe was recognized working based on the mechanism of internal charge transfer (ICT). In accordance with the hard soft acid base (HSAB) principle,
3 complexation of Hg2+ was most likely to involve the vinyl group. In the presence of Hg2+, the ICT effect from the N to the electronwithdrawing vinyl moiety was enhanced, which was facilitated by the mercuration of the vinyl moiety. This enhancement in ICT effect also afforded the reduced intensity and bathochromic shift of fluorescence as a function of Hg2+ concentration.
0.6
(a)
Hg2+/equiv 4.5 4.0 3.5 2.8 2.4 2.0 1.6 1.2 0.8 0.4 0
Absorbance
0.5
0.4
0.3
0.2
addition of Hg2+ resulted in the red shift of absorption and emission band, and it exhibited good selectivity. To the best of our knowledge, it’s the first fluorescent probe based on epindolidion, and derivatives of epindolidion, like other chromophores, showed great performance in solutions. Therefore, it’s reasonable to believe that derivatives of epindolidion would play more important roles in the fields of supramolecular research and synthesis of organic optoelectronic materials.
Acknowledgments This research was financially supported by the National Nature Science Foundation of China (21272069, 20672035), the Fundamental Research Funds for the Central Universities, Lily Group CO. LTD. and Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences.
0.1
References and notes 0.0 400
450
500
550
600
1.
Wavelength/nm
2. 3. 4. 8000
(b)
6000
Intensity/au
5. 6. 7.
Hg2+/equiv 4.5 4.0 3.5 2.8 2.4 2.0 1.6 1.2 0.8 0.4 0
7000
5000 4000 3000 2000
8. 9. 10. 11.
12.
1000 0 500
550
600
650
700
13.
Wavelength/nm
Figure 5 UV-Vis (a) and fluorescence (b) spectra of the probe (5×10-5 M) in CH3CN solution upon addition of increasing concentrations of Hg2+ at 25 oC, λex = 471 nm.
14.
15. 16. 17. 18. 19. 20. 21.
Figure 6 Plot of (a) the absorbance ratio of probe between 511 and 460 nm (A511 nm/A460 nm) and (b) the emission intensity ratio of probe between 574 and 485 nm (I574nm/I485 nm) vs concentration of Hg2+ in CH3CN.
3. Conclusion In summary, after a simple two-step synthesis, epindolidion, the “old dye”, became a new prototype of efficient colorimetric and fluorescent probes for Hg2+. For the receptor in CH3CN, the
Torre, G.; Claessens, C. G.; Torres, T. Chem. Commun. 2007, 2, 2000. Imahori, H.; Umeyama. T.; Ito, S. Acc. Chem. Res. 2009, 42, 1809. Qu, S.; Tian, H. Chem. Commun. 2012, 48, 3039. Babu, S. S.; Praveen, V. K.; Ajayaghosh, A. Chem. Rev. 2014, 114, 1973. Czarnic, A. W. Acc. Chem. Res. 1994, 27, 302. Zhou, Y.; Zhang, J. F.; Yoon, J. Chem. Rev. 2014, 114, 5511. Głowacki, E. D.; Voss, G.; and Sariciftci, N. S. Adv. Mater. 2013, 25, 6783. Farinola, G. M.; Ragni, R. Chem. Soc. Rev. 2011, 40, 3467. Edward, E.; Howard, M. J. Org. Chem. 1968, 33, 4004. Kim, C. K.; Maggiulli, C. A. J. Heterocycl. Chem. 1979, 16, 1651. Głowacki, E. D.; Irimia-Vladu, M.; Kaltenbrunner. M.; Gsiorowski, J.; White, M. S.; Monkowius, U.; Romanazzi, G.; Suranna, G. P.; Mastrorilli, P.; Sekitani, T.; Bauer, S.; Someya, T.; Torsi, L.; Sariciftci, N. S. Adv. Mater. 2013, 25, 1563. Głowacki, E, D.; Tangorra, R. R.; Coskun, H.; Farka, D.; Operamolla, A.; Kanbur, Y.; Milano, F.; Giotta, L.; Farinolab, G. M.; Sariciftcia, N. S. J. Mater. Chem. C 2015, 3, 6554. Głowacki, E. D.; Romanazzi, G.; Yumusak, C.; Coskun, H.; Monkowius, U.; Voss, G.; Burian, M.; Lechner, R. T.; Demitri, N.; Redhammer, G. J.; Sünger, N.; Suranna, G. P.; Sariciftci, S. Adv. Funct. Mater. 2015, 25, 776. Yang, C. Y.; Shi, K.; Lei, T. Wang, J.; Wang, X. Y.; Zhuang, F. D.; Wang, J. Y.; Pei, J. ACS Appl. Mater. Interfaces 2016, 8, 3714. Wang, L. M.; Cai, X. F.; Wang, F.; Wang, G. F.; Tian, H.; Chen, L. R.; Chen, L.; Huang, Z. CN 103145708, 2013. Zhang, G. J.; Li, H. Y.; Bi, S. M.; Song, L. F.; Lu, Y. X.; Zhang, L.; Yu, J. J.; Wang, L. M. Analyst 2013, 138, 6163. Chen, Z. J.; Wang, L. M.; Zou, G.; Cao, X. M.; Wu, Y.; Hu, P. J. Spectrochim. Acta. A 2013, 114, 323. Wu, S. Y.; Zhang, K. W.; Wang, Y. F.; Mao, D.; Liu, X.; Yu, J. J.; Wang, L. M. Tetrahedron Lett. 2014, 55, 351. Wang, Y. F.; Zhang, L.; Zhang, G. J.; Wu, Y.; Wu, S. Y.; Yu, J. J.; Wang, L. M. Tetrahedron Lett. 2014, 55, 3218. Culzoni, M. J.; Muñoz de la Peña; Machuca, A.; Goicoechea, H. C.; Babiano, R. Anal. Methods 2013, 5, 30. Solomons, T. W. G.; Fryhle, C. B. Organic Chemistry. 10th ed. John Wiley & Sons: New York, 2011.
Supplementary Material Supplementary data (these data include general information, characteristic data and copies of NMR spectra described in this Letter).
Graphical Abstract To create your abstract, type over the instructions in the template box below. Fonts or abstract dimensions should not be changed or altered.
Functionalization of Epindolidion: a New Colorimetric and Ratiometric Fluorescent Probe for Hg2+
Leave this area blank for abstract info.
Yue Wua, #, Xiaofei Caia, #, Shengying Wua, , Limin Wanga, , Guifeng Wangb and Feng Wangb
4
Tetrahedron Letters
Highlights 1.
A new epindolidion derivative applied as Hg2+ ion probe for the first time
2.
Colorimetric and ratiometric recognition with good selectivity and sensitivity
3.
Good linear property
S0040-4039(16)30745-6 http://dx.doi.org/10.1016/j.tetlet.2016.06.075 TETL 47802
To appear in:
Tetrahedron Letters
Received Date: Revised Date: Accepted Date:
12 April 2016 13 June 2016 17 June 2016
Please cite this article as: Wu, Y., Cai, X., Wu, S., Wang, L., Wang, G., Wang, F., Functionalization of Epindolidion: A New Colorimetric and Ratiometric Fluorescent Probe for Hg2+, Tetrahedron Letters (2016), doi: http://dx.doi.org/ 10.1016/j.tetlet.2016.06.075
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
1
Tetrahedron Letters j ou r n a l h o m ep a g e : w w w . e ls e vi e r . c o m
Functionalization of Epindolidion: a New Colorimetric and Ratiometric Fluorescent Probe for Hg2+ Yue Wua, #, Xiaofei Caia, #, Shengying Wua, , Limin Wanga, , Guifeng Wang b and Feng Wangb a
Shanghai Key Laboratory of Functional Materials Chemistry, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, China Lily Group CO. LTD, Nong Yi Chang Town, Linjiang Industrial Park, Xiaoshan Dis., Hangzhou City, Zhejiang Province 311228, China # These authors contributed equally to this work b
A RT I C L E I N F O
A BS T RA C T
Article history: Received Received in revised form Accepted Available online
After functionalization, a new epindolidion derivative bearing a vinyl group was synthesized as a naked-eye fluorescent probe for Hg 2+ through two steps. The probe showed good selectivity to Hg2+ over other metal cations in CH 3CN. On the basis of the addition of Hg2+, the fluorescence emission of the probe at 485 nm was ratio quenched along with the appearance of the new peak at 574 nm. Simultaneously, the absorbance of the probe showed bathochromic shift as a function of the increasing concentration of Hg2+. All of the features mentioned make this compound a useful probe for Hg2+ measurement. To the best of our knowledge, it’s the first fluorescent probe based on epindolidion.
Keywords: Epindolidion derivative Mercury ion Colorimetric Ratiometric fluorescent Probe
1. Introduction Many kinds of dyes and pigments have been functionalized into molecular devices and advanced materials, making “old dyes” into “new materials”1. For instance, derivatives of chromophores, such as naphthalimide, peryleneimide, coumarin, quinacridone and diketopyrrolopyrrole, were widely introduced into photovoltaic materials2-3, organic soft materials4, fluorescent chemosensors5-6 and other functional materials7-8. Epindolidion and its derivatives are a class of brilliant yellow pigments with strong fluorescence and show high performance, such as exceptional light, weather and heat stability for the intermolecular hydrogen bond7, 9-11. For a long time chemists have focused considerable and consistent attentions on their synthesis and pigment performance, and only a few researches were reported on functionalization of epindolidions, making them to be wonderful potential materials for organic semiconductors, Field-Effect Transistors and Light-Emitting Diodes12-14. Based on exploration about synthesis optimizing of epindolidions in our group15, it is meaningful to do more researches on the fluorescence features of epindolidions in solution to widen their applications. Following our interest on chemosensors of different chromophores16-19, a derivative of epindolidion with good solubility was designed as a “naked-eye” colorimetric and ratiometric fluorescent probe for mercury ions. As one of the most toxic heavy metal elements, mercury can lead to the
———
2009 Elsevier Ltd. All rights reserved .
dysfunction of the organism, so there is an increasing interest in the design and development of chemical probes for mercury ion20. Moreover, to the best of our knowledge, there are no reports on the fluorescent probes based on epindolidion derivatives. Herein, a new epindolidion derivative was designed and synthesized, with an allyl group contacted on the N atom as Hg2+ receptor based on mercuration reaction 21. The chemosensor 3 (Scheme 1) in this paper was found to be effectively colorimetric and ratiometric fluorescent probes for naked-eye detection of Hg2+.
Scheme 1 Synthetic routes of Epindolidion derivatives.
Corresponding author. Tel.: +86-021-6425-3881; fax: +86-021-6425-3881; e-mail: [email protected] Corresponding author. Tel.: +86-021-6425-3881; fax: +86-021-6425-3881; e-mail: [email protected]
2
Tetrahedron Letters 2. Results and discussion
2.1. Synthesis of compound 3 Compound 3 was synthesized by a two-step procedure from epindolidion (Scheme 1), and the final products were obtained after purified by silica gel chromatography (see details in ESI†). 2.2. Colorimetric and Ratiometric Fluorescent Probe of Fluoride Ions In order to obtain a naked-eye result, the probe was examined at the concentration of 5×10-5 M. The selectivity of the probe toward Hg2+ over other competitive species was investigated in the presence of various biologically and environmentally relevant metal ions. All the measurements were conducted by using the chloride metal ion in aqueous buffer. Among the various metal ions tested, the probe detected Hg 2+ while other relevant metals did not modulate the absorption and fluorescence spectrum (Figure 1 (a), (b)). Thus, the probe seemed to be useful for selectively sensing, even with these relevant analytes.
0.6
(a)
probe,probe+Pb2+,Zn2+,Cd2+,Ag+, Ni2+,Cu2+,Fe2+,Cr3+,Mn2+,Co2+,Ca2+, Mg2+,K+,Na+
Absorbance
0.5
Figure 2 The fluorescence emission response of the probe (5×10-5 M) on addition of 5×10-5 M cations in the form of chloride salts in aqueous solution of acetonitrile excited at 365 nm using UV lamp.( Left to right: probe, probe + Hg2+, Pb2+, Zn2+, Cd2+, Ag+, Ni2+, Cu2+, Fe2+, Cr3+, Mn2+, Co2+, Ca2+, Mg2+, K+, Na+.)
Figure 3 1H NMR spectra of “probe” and “probe+Hg2+” .
0.4
probe+Hg2+
0.3
0.2
0.1
Figure 4 The mass spectrometry analysis of the complexation probe-[HgCl]+.
0.0 400
450
500
550
600
Wavelength/nm
18000
(b)
16000
probe,probe+Pb2+,Zn2+,Cd2+,Ag+, Ni2+,Cu2+,Fe2+,Cr3+,Mn2+,Co2+,Ca2+, Mg2+,K+,Na+
Intensity/au
14000 12000
The molecular behavior was studied by 1H NMR and mass spectrometry. In the 1H NMR spectra of “probe+Hg2+”, signals of the aromatic protons dramatically changed, and signals of H1, H2 and H3 were found at d = 4.0-5.5 ppm (Figure 3). Both mass spectrometry analysis (m/z 707.2057) and the 1H NMR spectra indicated the formation of onium ions21 (Scheme 2, Figures 3-4).
10000 8000 6000 4000
probe+Hg2+
2000 0 500
Scheme 2 The proposed binding mode of compound 3 and Hg2+.
550
600
650
700
Wavelength/nm
Figure 1 UV-Vis (a) and fluorescence (b) spectra of the probe (5×10-5 M) in CH3CN in the presence of different metal ions at 25 oC, λex = 471 nm.
Notably, the red shift combined with large ratiometric absorbtion and fluorescent response rendered the probe suitable for detection of Hg2+ by simple visual inspection (Figure 2). However, the competition between Hg2+ and other metals showed no significant quenching in the sample. The reason might be that the redundant anions caused equilibrium shifted from more reactive [HgCl]+ to less reactive HgCl2.
Upon progressive addition of Hg2+, the maximum absorption wavelength of the probe at 460 nm was decreased gradually, meanwhile the new absorbance wavelength (511 nm) of the maximum could be observed and increased (Figure 5(a)). Also, from the clear isosbestic points at 471 nm, it indicated the formation of new compound. Excited at 471 nm, the free probe showed an intense emission at 485 nm, however, the addition of Hg2+ led to a drastic decrease at 485 nm and simultaneous appearance of a new emission band at 574 nm, as showed in the Figure 5(b). As a result, the probe performed as a colorimetric and ratiometric fluorescent probe (Figure 6(a), (b)). From the evidence above, the probe was recognized working based on the mechanism of internal charge transfer (ICT). In accordance with the hard soft acid base (HSAB) principle,
3 complexation of Hg2+ was most likely to involve the vinyl group. In the presence of Hg2+, the ICT effect from the N to the electronwithdrawing vinyl moiety was enhanced, which was facilitated by the mercuration of the vinyl moiety. This enhancement in ICT effect also afforded the reduced intensity and bathochromic shift of fluorescence as a function of Hg2+ concentration.
0.6
(a)
Hg2+/equiv 4.5 4.0 3.5 2.8 2.4 2.0 1.6 1.2 0.8 0.4 0
Absorbance
0.5
0.4
0.3
0.2
addition of Hg2+ resulted in the red shift of absorption and emission band, and it exhibited good selectivity. To the best of our knowledge, it’s the first fluorescent probe based on epindolidion, and derivatives of epindolidion, like other chromophores, showed great performance in solutions. Therefore, it’s reasonable to believe that derivatives of epindolidion would play more important roles in the fields of supramolecular research and synthesis of organic optoelectronic materials.
Acknowledgments This research was financially supported by the National Nature Science Foundation of China (21272069, 20672035), the Fundamental Research Funds for the Central Universities, Lily Group CO. LTD. and Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences.
0.1
References and notes 0.0 400
450
500
550
600
1.
Wavelength/nm
2. 3. 4. 8000
(b)
6000
Intensity/au
5. 6. 7.
Hg2+/equiv 4.5 4.0 3.5 2.8 2.4 2.0 1.6 1.2 0.8 0.4 0
7000
5000 4000 3000 2000
8. 9. 10. 11.
12.
1000 0 500
550
600
650
700
13.
Wavelength/nm
Figure 5 UV-Vis (a) and fluorescence (b) spectra of the probe (5×10-5 M) in CH3CN solution upon addition of increasing concentrations of Hg2+ at 25 oC, λex = 471 nm.
14.
15. 16. 17. 18. 19. 20. 21.
Figure 6 Plot of (a) the absorbance ratio of probe between 511 and 460 nm (A511 nm/A460 nm) and (b) the emission intensity ratio of probe between 574 and 485 nm (I574nm/I485 nm) vs concentration of Hg2+ in CH3CN.
3. Conclusion In summary, after a simple two-step synthesis, epindolidion, the “old dye”, became a new prototype of efficient colorimetric and fluorescent probes for Hg2+. For the receptor in CH3CN, the
Torre, G.; Claessens, C. G.; Torres, T. Chem. Commun. 2007, 2, 2000. Imahori, H.; Umeyama. T.; Ito, S. Acc. Chem. Res. 2009, 42, 1809. Qu, S.; Tian, H. Chem. Commun. 2012, 48, 3039. Babu, S. S.; Praveen, V. K.; Ajayaghosh, A. Chem. Rev. 2014, 114, 1973. Czarnic, A. W. Acc. Chem. Res. 1994, 27, 302. Zhou, Y.; Zhang, J. F.; Yoon, J. Chem. Rev. 2014, 114, 5511. Głowacki, E. D.; Voss, G.; and Sariciftci, N. S. Adv. Mater. 2013, 25, 6783. Farinola, G. M.; Ragni, R. Chem. Soc. Rev. 2011, 40, 3467. Edward, E.; Howard, M. J. Org. Chem. 1968, 33, 4004. Kim, C. K.; Maggiulli, C. A. J. Heterocycl. Chem. 1979, 16, 1651. Głowacki, E. D.; Irimia-Vladu, M.; Kaltenbrunner. M.; Gsiorowski, J.; White, M. S.; Monkowius, U.; Romanazzi, G.; Suranna, G. P.; Mastrorilli, P.; Sekitani, T.; Bauer, S.; Someya, T.; Torsi, L.; Sariciftci, N. S. Adv. Mater. 2013, 25, 1563. Głowacki, E, D.; Tangorra, R. R.; Coskun, H.; Farka, D.; Operamolla, A.; Kanbur, Y.; Milano, F.; Giotta, L.; Farinolab, G. M.; Sariciftcia, N. S. J. Mater. Chem. C 2015, 3, 6554. Głowacki, E. D.; Romanazzi, G.; Yumusak, C.; Coskun, H.; Monkowius, U.; Voss, G.; Burian, M.; Lechner, R. T.; Demitri, N.; Redhammer, G. J.; Sünger, N.; Suranna, G. P.; Sariciftci, S. Adv. Funct. Mater. 2015, 25, 776. Yang, C. Y.; Shi, K.; Lei, T. Wang, J.; Wang, X. Y.; Zhuang, F. D.; Wang, J. Y.; Pei, J. ACS Appl. Mater. Interfaces 2016, 8, 3714. Wang, L. M.; Cai, X. F.; Wang, F.; Wang, G. F.; Tian, H.; Chen, L. R.; Chen, L.; Huang, Z. CN 103145708, 2013. Zhang, G. J.; Li, H. Y.; Bi, S. M.; Song, L. F.; Lu, Y. X.; Zhang, L.; Yu, J. J.; Wang, L. M. Analyst 2013, 138, 6163. Chen, Z. J.; Wang, L. M.; Zou, G.; Cao, X. M.; Wu, Y.; Hu, P. J. Spectrochim. Acta. A 2013, 114, 323. Wu, S. Y.; Zhang, K. W.; Wang, Y. F.; Mao, D.; Liu, X.; Yu, J. J.; Wang, L. M. Tetrahedron Lett. 2014, 55, 351. Wang, Y. F.; Zhang, L.; Zhang, G. J.; Wu, Y.; Wu, S. Y.; Yu, J. J.; Wang, L. M. Tetrahedron Lett. 2014, 55, 3218. Culzoni, M. J.; Muñoz de la Peña; Machuca, A.; Goicoechea, H. C.; Babiano, R. Anal. Methods 2013, 5, 30. Solomons, T. W. G.; Fryhle, C. B. Organic Chemistry. 10th ed. John Wiley & Sons: New York, 2011.
Supplementary Material Supplementary data (these data include general information, characteristic data and copies of NMR spectra described in this Letter).
Graphical Abstract To create your abstract, type over the instructions in the template box below. Fonts or abstract dimensions should not be changed or altered.
Functionalization of Epindolidion: a New Colorimetric and Ratiometric Fluorescent Probe for Hg2+
Leave this area blank for abstract info.
Yue Wua, #, Xiaofei Caia, #, Shengying Wua, , Limin Wanga, , Guifeng Wangb and Feng Wangb
4
Tetrahedron Letters
Highlights 1.
A new epindolidion derivative applied as Hg2+ ion probe for the first time
2.
Colorimetric and ratiometric recognition with good selectivity and sensitivity
3.
Good linear property