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 calixpyrrole, 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 calixpyrrole derivative proved to be the most efficient molecular receptor for anions, while the calixpyrrole 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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