2-(4'-Pyridyl-N-oxide)-Substituted Hemithioindigos as Photoresponsive Guests for a Super Aryl-Extended Calix[4]pyrrole Receptor

Abstract

We report the synthesis of two 2-(4'-pyridyl-N-oxide)-substituted hemithioindigos (HTIs). We probed their photoisomerization by using UV/Vis and ¹ H NMR spectroscopy techniques. Light irradiation at λ=450 nm provoked the isomerization of the HTI Z isomer to the E counterpart to a large extent (≈80 % at the photostationary state). ¹ H NMR titration experiments revealed the formation of thermodynamically and kinetically stable 1:1 inclusion complexes of the (Z)-HTI isomers with a super aryl-extended host (association constant>10⁴ m^-1 ). Photoirradiation at λ=450 nm of the inclusion complexes induced the isomerization of the bound HTI N-oxide to afford the (E)-HTI⊂calix[4]pyrrole complex. We determined accurate association constant values for the 1:1 inclusion complexes of the (Z)- and (E)-HTI isomers by using isothermal titration calorimetry experiments. The results showed that the stability constants of the (E)-HTI complexes were 2.2-2.8-fold lower than those of the (Z)-HTI counterparts, which explains the lack of light-induced release of the former to the bulk solution.

Keywords: calixarenes; hemithioindigos; molecular recognition; photoisomerization; supramolecular chemistry.