Indigo and Hemiindigo-Based Photoswitchable Hydrogen Bond Arrays

Photochromic molecular subunits capable of supramolecular complexation mediated by hydrogen bonds have the potential to produce materials with novel and dynamic light responsive properties. This thesis reports on the synthesis and photochemical and complexation characterization of seven hemiindigo-based compounds. Furthermore, the ability of indigo to act as a complementary hydrogen bond array is discussed along with the subsequent synthesis and photochemical/physical characterization of a self-associating indigo based hydrogen bond array. Poor to excellent photochemical/physical properties were observed for the photoswitchable hemiindigo and indigo derivative(s) where complexation has been found to be limited. Indigo has been shown to act as an AA array in the presence of various HBD (hydrogen bond donor) arrays. The potential of these compounds to then be incorporated into polymers to make supramolecular polymers and subsequent materials with dynamic light responsive properties will be discussed

Synthesis of Hexahydropyridazines by [4 + 2] Cycloaddition of Donor-Acceptor Cyclobutanes and

The GaCl3-catalyzed [4+2] cycloaddition between alkoxy- and aryl-activated donor-acceptor cyclobutane diesters and cis-diazene 1a (4-phenyl-1,2,4-triazoline-3,5-dione, PTAD) is disclosed. The reaction provides hexahydropyridazine derivatives as single diastereomers in good to excellent yields in most cases. Structural assignment of the cycloadduct 3b was unambiguously established by single crystal X-ray diffraction