Fluorescence Polymer Incorporating Triazole and Benzo[2,1,3]thiadiazole Moieties for Ni^²+ Detection

Abstract

Conjugated polymer could be obtained by the polymerization of 4,7-diethynylbenzo[2,1,3]thiadiazole (M-1) with 1,4-diazidobenzene (M-2) via click reaction. The polymer shows strong blue-green fluorescence due to the extended π-electronic structure in the main chain backbone. The responsive optical properties of the polymer on various transition metal ions were investigated by fluorescence spectroscopy. Compared with other transition metal cations, such as Co^²+, Hg^²+, Ag⁺, Cd^²+, Cu^²+ and Zn^²+, Ni^²+ showed the most pronounced fluorescence response in the presence of the conjugated polymer. The results indicate this kind of polymer with benzo[2,1,3]thiadiazole and triazole units can be used as a selective fluorescence sensor for Ni^²+ detection.

conjugated polymer - click reaction - fluorescence sensor - nickel ion detection

References and Notes

<A NAME="RW04110ST-1A">1a</A> McQuade DT. Pullen AE. Swager TM. Chem. Rev.  2000,  100:  2537 

<A NAME="RW04110ST-1B">1b</A> Thomas SW. Joly GD. Swager TM. Chem. Rev.  2007,  107:  1339 

<A NAME="RW04110ST-2A">2a</A> Nolan EM. Lippard SJ. Chem. Rev.  2008,  108:  3443 

<A NAME="RW04110ST-2B">2b</A> Kim IB. Dunkhorst A. Gilbert J. Bunz UHF. Macromolecules  2005,  38:  4560 

<A NAME="RW04110ST-2C">2c</A> Fan L.-J. Jones WE. J. Am. Chem. Soc.  2006,  128:  6784 

<A NAME="RW04110ST-3A">3a</A> Ashton WM. Nature (London)  1972,  237:  46 

<A NAME="RW04110ST-3B">3b</A> Prophete C. Carlson EA. Li Y. Duffy J. Steinetz B. Lasano S. Zelikoff JT. Fish Shellfish Immunol.  2006,  21:  325 

<A NAME="RW04110ST-4A">4a</A> Lin W. Yuan L. Cao Z. Feng J. Feng Y. Dyes Pigments  2009,  83:  14 

<A NAME="RW04110ST-4B">4b</A> Maisonneuve S. Fang Q. Xie J. Tetrahedron  2008,  64:  8716 

<A NAME="RW04110ST-4C">4c</A> Chattopadhyay N. Mallick A. Sengupta S. J. Photochem. Photobiol. A: Chem.  2006,  177:  55 

<A NAME="RW04110ST-4D">4d</A> Grabchev I. Chovelon J.-M. Nedelcheva A. J. Photochem. Photobiol. A: Chem.  2006,  183:  9 

<A NAME="RW04110ST-4E">4e</A> Xiao Y. Qian X. Tetrahedron Lett.  2003,  44:  2087 

<A NAME="RW04110ST-5A">5a</A> Zhang Y. Murphy CB. Jones WE. Macromolecules  2002,  35:  630 

<A NAME="RW04110ST-5B">5b</A> Feng J. Li Y. Yang M. J. Polym. Sci. Part A: Polym. Chem.  2009,  47:  222 

<A NAME="RW04110ST-5C">5c</A> Liu Y. Zhang S. Miao Q. Zheng L. Zong L. Cheng Y. Macromolecules  2007,  40:  4839 

<A NAME="RW04110ST-5D">5d</A> Huang X. Xu Y. Miao Q. Zong L. Hu H. Cheng Y. Polymer  2009,  50:  2793 

<A NAME="RW04110ST-6A">6a</A> Kolb HC. Finn MG. Sharpless KB. Angew. Chem. Int. Ed.  2001,  40:  2004 

<A NAME="RW04110ST-6B">6b</A> Rostovtsev VV. Green LG. Fokin VV. Sharpless KB. Angew. Chem. Int. Ed.  2002,  41:  2596 

<A NAME="RW04110ST-7A">7a</A> Droumaguet BL. Velonia K. Macromol. Rapid. Commun.  2008,  29:  1073 

<A NAME="RW04110ST-7B">7b</A> Lundberg P. Hawker CJ. Hult A. Malkoch M. Macromol. Rapid. Commun.  2008,  29:  998 

<A NAME="RW04110ST-7C">7c</A> Binder WH. Sachsenhofer R. Macromol. Rapid. Commun.  2008,  29:  952 

<A NAME="RW04110ST-7D">7d</A> Lodge TP. Macromolecules  2009,  42:  3827 

<A NAME="RW04110ST-8">8</A> Tamanini E. Katewa A. Sedger LM. Todd MH. Watkinson M. Inorg. Chem.  2009,  48:  319 

<A NAME="RW04110ST-9">9</A> Zheng L. Huang X. Shen Y. Cheng Y. Synlett  2010,  453 

<A NAME="RW04110ST-10A">10a</A> Huang X. Xu Y. Zhen L. Meng J. Cheng Y. Polymer  2009,  50:  5996 

<A NAME="RW04110ST-10B">10b</A> Huang X. Meng J. Dong Y. Cheng Y. Zhu C. J. Polym. Sci. Part A: Polym. Chem.  2010,  48:  997 

<A NAME="RW04110ST-10C">10c</A> Liu X. Zhu J. J. Phys. Chem. B  2009,  113:  8214 

<A NAME="RW04110ST-10D">10d</A> Liu S. Fang C. Zhao Q. Fan Q. Huang W. Macromol. Rapid Commun.  2008,  29:  1212 

<A NAME="RW04110ST-11">11</A> Neto BAD. Lopes AS. Ebeling G. Goncalves RS. Costa VEU. Quina FH. Dupont J. Tetrahedron  2005,  61:  10975 

<A NAME="RW04110ST-12">12</A> Minato M. Lahti PM. J. Am. Chem. Soc.  1997,  119:  2187 

<A NAME="RW04110ST-13">13</A> Karim MA. Cho Y. Park JS. Ryu TI. Lee MJ. Song M. Jin S. Lee JW. Gal Y. Macromol. Chem. Phys.  2008,  209:  1967 

<A NAME="RW04110ST-14">14</A>

Procedure for the Chiral Polymer: A mixture of M-1 (73.60 mg, 0.40 mmol), M-2 (64.00 mg, 0.40 mmol), 10 mol% sodium ascorbate (7.92 mg, 0.040 mmol) and 5 mol% Cu₂SO₄˙5H₂O (4.99 mg, 0.020 mmol) was dissolved in a solvent mixture: THF (10 mL), t-BuOH (10 mL), and H₂O (10 mL). The solution was stirred at 30-36 ˚C for 2 d under N₂. The solvents were removed under reduced pressure and the residue was extracted with CHCl₃ (2 × 50 mL). The organic layer was washed with an aq NH₄OH solution, H₂O and then dried over anhyd Na₂SO₄. After the solution was removed, the resulting polymer was precipitated into MeOH, and then filtered and washed with MeOH several times. Further purification could be conducted by dissolving the polymer in CHCl₃ to precipitate in MeOH again. The polymer was dried in vacuum to give a yellow solid (100.01 mg, 72.2% yield). Polymer spectroscopic data: ^¹H NMR (300 MHz, CDCl₃): δ = 9.35 (s, 1 H), 9.22 (s, 1 H), 8.70-8.82 (m, 2 H), 7.92-8.20 (m, 4 H). FT-IR (KBr): 2960, 2923, 2094, 1521, 1239, 1038 cm^-¹. Anal. Calcd for C₁₆H₈N₈S: C, 55.81; H, 2.34; N, 32.54. Found: C, 54.68; H, 2.12; N, 31.29.

<A NAME="RW04110ST-15A">15a</A> Justin KR. Lin JT. Velusamy M. Tao Y.-T. Chuen C.-H. Adv. Funct. Mater.  2004,  14:  83 

<A NAME="RW04110ST-15B">15b</A> Zhang X. Gorohmaru H. Kadowaki M. Kobayashi T. Ishi-i T. Thiemann T. Mataka S. J. Mater. Chem.  2004,  14:  1901