Synthesis and recognition properties of higher order tetrathiafulvalene (TTF) calix[n]pyrroles (n = 4-6)

Jung Su Park, Christopher Bejger, Karina R. Larsen, Kent A. Nielsen, Atanu Jana, Vincent M. Lynch, Jan O. Jeppesen, Dongho Kim, Jonathan L. Sessler

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Abstract

Two new benzoTTF-annulated calix[n]pyrroles (n = 5 and 6) were synthesized via a one-step acid catalyzed condensation reaction and fully characterized via single crystallographic analyses. As compared to the known tetra-TTF annulated calix[4]pyrrole, which is also produced under the conditions of the condensation reaction, the expanded calix[n]pyrroles (n = 5 and 6) are characterized by a larger cavity size and a higher number of TTF units (albeit the same empirical formula). Analysis of the binding isotherms obtained from UV-Vis spectroscopic titrations carried out in CHCl 3 in the presence of both anionic (Cl -, Br -, I -, CH 3COO -, H 2PO 4 -, and HSO 4 -) and neutral (1,3,5-trinitrobenzene (TNB) and 2,4,6-trinitrotoluene (TNT)) substrates revealed that as a general rule the calix[6]pyrrole derivative proved to be the most efficient molecular receptor for anions, while the calix[4]pyrrole congener proves most effective for the recognition of TNB and TNT. These findings are rationalized in terms of the number of electron rich TTF subunits and NH hydrogen bond donor groups within the series, as well as an ability to adopt conformations suitable for substrate recognition, and are supported by solid state structural analyses.

Original languageEnglish
Pages (from-to)2685-2689
Number of pages5
JournalChemical Science
Volume3
Issue number9
DOIs
Publication statusPublished - 2012 Sep 1

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Trinitrotoluene
Pyrroles
Condensation reactions
Substrates
Titration
Anions
Isotherms
Conformations
Hydrogen bonds
Derivatives
Acids
Electrons
tetrathiafulvalene
sym-trinitrobenzene
calix(4)pyrrole
tetrathiafulvalene calix(4)pyrrole
calix(6)pyrrole

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

Park, J. S., Bejger, C., Larsen, K. R., Nielsen, K. A., Jana, A., Lynch, V. M., ... Sessler, J. L. (2012). Synthesis and recognition properties of higher order tetrathiafulvalene (TTF) calix[n]pyrroles (n = 4-6). Chemical Science, 3(9), 2685-2689. https://doi.org/10.1039/c2sc20636f
Park, Jung Su ; Bejger, Christopher ; Larsen, Karina R. ; Nielsen, Kent A. ; Jana, Atanu ; Lynch, Vincent M. ; Jeppesen, Jan O. ; Kim, Dongho ; Sessler, Jonathan L. / Synthesis and recognition properties of higher order tetrathiafulvalene (TTF) calix[n]pyrroles (n = 4-6). In: Chemical Science. 2012 ; Vol. 3, No. 9. pp. 2685-2689.
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abstract = "Two new benzoTTF-annulated calix[n]pyrroles (n = 5 and 6) were synthesized via a one-step acid catalyzed condensation reaction and fully characterized via single crystallographic analyses. As compared to the known tetra-TTF annulated calix[4]pyrrole, which is also produced under the conditions of the condensation reaction, the expanded calix[n]pyrroles (n = 5 and 6) are characterized by a larger cavity size and a higher number of TTF units (albeit the same empirical formula). Analysis of the binding isotherms obtained from UV-Vis spectroscopic titrations carried out in CHCl 3 in the presence of both anionic (Cl -, Br -, I -, CH 3COO -, H 2PO 4 -, and HSO 4 -) and neutral (1,3,5-trinitrobenzene (TNB) and 2,4,6-trinitrotoluene (TNT)) substrates revealed that as a general rule the calix[6]pyrrole derivative proved to be the most efficient molecular receptor for anions, while the calix[4]pyrrole congener proves most effective for the recognition of TNB and TNT. These findings are rationalized in terms of the number of electron rich TTF subunits and NH hydrogen bond donor groups within the series, as well as an ability to adopt conformations suitable for substrate recognition, and are supported by solid state structural analyses.",
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Park, JS, Bejger, C, Larsen, KR, Nielsen, KA, Jana, A, Lynch, VM, Jeppesen, JO, Kim, D & Sessler, JL 2012, 'Synthesis and recognition properties of higher order tetrathiafulvalene (TTF) calix[n]pyrroles (n = 4-6)', Chemical Science, vol. 3, no. 9, pp. 2685-2689. https://doi.org/10.1039/c2sc20636f

Synthesis and recognition properties of higher order tetrathiafulvalene (TTF) calix[n]pyrroles (n = 4-6). / Park, Jung Su; Bejger, Christopher; Larsen, Karina R.; Nielsen, Kent A.; Jana, Atanu; Lynch, Vincent M.; Jeppesen, Jan O.; Kim, Dongho; Sessler, Jonathan L.

In: Chemical Science, Vol. 3, No. 9, 01.09.2012, p. 2685-2689.

Research output: Contribution to journalArticle

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T1 - Synthesis and recognition properties of higher order tetrathiafulvalene (TTF) calix[n]pyrroles (n = 4-6)

AU - Park, Jung Su

AU - Bejger, Christopher

AU - Larsen, Karina R.

AU - Nielsen, Kent A.

AU - Jana, Atanu

AU - Lynch, Vincent M.

AU - Jeppesen, Jan O.

AU - Kim, Dongho

AU - Sessler, Jonathan L.

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N2 - Two new benzoTTF-annulated calix[n]pyrroles (n = 5 and 6) were synthesized via a one-step acid catalyzed condensation reaction and fully characterized via single crystallographic analyses. As compared to the known tetra-TTF annulated calix[4]pyrrole, which is also produced under the conditions of the condensation reaction, the expanded calix[n]pyrroles (n = 5 and 6) are characterized by a larger cavity size and a higher number of TTF units (albeit the same empirical formula). Analysis of the binding isotherms obtained from UV-Vis spectroscopic titrations carried out in CHCl 3 in the presence of both anionic (Cl -, Br -, I -, CH 3COO -, H 2PO 4 -, and HSO 4 -) and neutral (1,3,5-trinitrobenzene (TNB) and 2,4,6-trinitrotoluene (TNT)) substrates revealed that as a general rule the calix[6]pyrrole derivative proved to be the most efficient molecular receptor for anions, while the calix[4]pyrrole congener proves most effective for the recognition of TNB and TNT. These findings are rationalized in terms of the number of electron rich TTF subunits and NH hydrogen bond donor groups within the series, as well as an ability to adopt conformations suitable for substrate recognition, and are supported by solid state structural analyses.

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