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A chloride-anion insensitive colorimetric chemosensor for trinitrobenzene and picric acid

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Abstract

A new receptor, the bisTTF-calix[2]thiophene[2]pyrrole derivative 3, has been prepared from the Lewis acid-catalyzed condensation of 2,5-bis(1-hydroxymethylethyl)thiopheno-TTF and pyrrole. This new system is found to form complexes with the electron-deficient guests, trinitrobenzene (TNB) and picric acid (PA), which serve as models for nitroaromatic explosives. The binding phenomenon, which has been studied in organic solution using proton nuclear magnetic resonance and absorption spectroscopies, results in an easy-to-visualize color change in chloroform that is independent of the presence of chloride anion, a known interferant for an earlier tetrakisTTF-calix[4]pyrrole TNB chemosensor. Support for the proposed binding mode comes from a preliminary solid state structure of the complex formed from TNB, namely TNB⊂3. A color change is also observed when dichloromethane solutions of chemosensor 3 are added to solvent-free samples of TNB, PA, and 2,4,6-trinitrotoluene supported on silica gel.

A new bis-tetrathiafulvalene calix[2]thiophene[2]pyrrole derivative has been prepared that gives rise to an easy-to-visualize color change in the presence of the model nitroaromatic explosives trinitrobenzene and picric acid.

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Notes

  1. TNB is free of any notable absorption features at λ ≥ 500 nm. Addition of 1 equiv. of TNB to a CH2Cl2 solution containing 1 mM 2 did not give any notable CT band.

  2. Crystallographic summary for 3. Large yellow prisms were grown by vapor diffusion of hexanes into a dichloromethane solution of the macrocycle, monoclinic, P21/c (No. 14), Z = 4 in a cell of dimensions: a = 18.8923(5), b = 14.1621(4), c = 20.1768(6) Å, β = 96.518(2)°, V = 5,363.5(3) Å3, ρ calc = 1.38 g cm−3, μ = 0.602 mm−1, F(000) = 2,336. Data were collected on a Nonus Kappa CCD using graphite monochromatized Mo Kα radiation (λ = 0.71073 Å) at −120 °C. The structure was refined on F 2 to an R w = 0.133, with a conventional R = 0.0492 (9,272 reflections with F o > 4[σ(F o)]), and a goodness of fit = 1.02 for 594 refined parameters. Further details of this structure are available from Cambridge Crystallographic Data Centre by referencing CCDC no. 720250.

  3. Crystallographic summary for TNB⊂3. Large prisms were grown by vapor diffusion of hexanes into a dichloromethane solution of the TNB⊂3, triclinic, P-1 (No. 2), Z = 2 in a cell of dimensions: a = 10.5476(5), b = 15.1626(8), c = 20.2972(1) Å, α = 95.174(2), β = 90.329(2), γ = 108.171(2)°, V = 3,069.7(3) Å3, ρ calc = 1.43 cm−3, μ = 0.547 mm−1, F(000) = 1,384. Data were collected on a Nonus Kappa CCD using graphite monochromatized Mo Kα radiation (λ = 0.71073 Å) at −120 °C. The structure was refined on F 2 to an R w  = 0.262, with a conventional R = 0.136 (13,337 reflections with F o > 4[σ(F o)]), and a goodness of fit = 3.12 for 786 refined parameters. Further details of this structure are available from Cambridge Crystallographic Data Centre by referencing CCDC no. 720251.

  4. The distance from the center of each of the disordered TNB phenyl rings to the least-squares plane through the TTF as defined by the positions of the S atoms are as follows: TNB phenyl ring orientation defined by C1a, C2a, C3a, C4a, C5a, and C6a to the least-squares plane through S2, S3, S4, S5, S6, and S7, 3.31(1) Å; TNB phenyl ring containing C1a, C2a, C3a, C4a, C5a, and C6a to the least-squares plane through S9, S10, S11, S12, S13, and S14, 3.53(1) Å; the other orientation of TNB defined by C1aa, C2aa, C3aa, C4aa, C5aa, and C6aa to the least-squares plane through S2, S3, S4, S5, S6, and S7, 3.49(1) Å; this latter plane to the plane defined by S9, S10, S11, S12, S13, and S14, 3.36(1) Å.

  5. The data were fitted to a 1:1 or 1:2 binding profile according to the method of Conners using the changes in the resonance associated with the pyrrole NH protons in the 1H NMR spectra [24].

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Acknowledgements

This work was supported by the NSF-CBET (grant no. 0730053 to JLS), the Korea Research Foundation Grant funded by the Korean Government (MOEHRD) (KRF-2007-357-C00061 to D-SK), the Strategic Research Council in Denmark through the Young Researchers Programme (project no. 2117-05-0115 to JOJ), the Strategic Research Council in Denmark through the Programme for Nanoscience, Technology, Biotechnology, and IT (project no. 2106-07-0031 to JOJ), the Danish Natural Science Research Council (FNU, projects no. 272-08-0047 to KAN and no. 272-08-0578 to JOJ). Mr. Jung Su Park and Dr. Franck Le Derf are also acknowledged for helpful discussions and advice.

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Correspondence to Jan O. Jeppesen or Jonathan L. Sessler.

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Kim, DS., Lynch, V.M., Nielsen, K.A. et al. A chloride-anion insensitive colorimetric chemosensor for trinitrobenzene and picric acid. Anal Bioanal Chem 395, 393–400 (2009). https://doi.org/10.1007/s00216-009-2819-4

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