(Digital Presentation) Photopolymerization of Tetraazaporphyrin Based Surfactants and Mesogens

Intermolecular interactions between tetraazaporphyrin (TAP) macrocycles are less dominated by π-π stacking interactions than interactions between their larger phthalocyanine derivatives. Consequently, the self-organization and -assembly of TAPs is more widely altered by changes to the type of complexed metal ion and substitution pattern. Presented here are different molecular designs for mesomorphic and amphiphilic TAPs that could be cross-linked by “click” chemistry and by the photo and thermal polymerization of diacetylene groups. All compounds were studied by polarized optical microscopy, thermal analysis, and X-ray diffraction to probe their (meso)phase structures and transitions and by the Langmuir-Blodget method to quantify their interfacial properties. Potential applications for these compounds include their use as active materials in sensors, functional coatings for metal oxide nanoparticles, and building blocks for dye nanoparticles. Topochemical Polymerization of a Nematic Tetraazaporphyrin Derivative to Generate Soluble Polydiacetylene Nanowires. M. Nazir Tahir, et al., 2019, Langmuir, 35(47) 15158−15167. Self-organization of Porphyrins and Phthalocyanines in two and three dimensions by S. Holger Eichhorn and Elmahdy Abdulhamied, in “Handbook of Porphyrin Science: Towards Tuned Properties of Porphyrinoids”, Vol. 42, Karl M. Kadish, Kevin M. Smith, Roger Guilard, Eds., World Scientific, Singapore, 2016, 173-232. Cross-linking of discotic tetraazaporphyrin dyes in 2 and 3 dimensions by “click” chemistry. Himadri Kayal, et al., 2013, J. Mater. Chem. C, 1(42), 7064-7072. Face- and edge-on orientations of octa-acid and -alcohol substituted tetraazaporphyrins in langmuir and Langmuir-Blodgett monolayers. M. M. Ahmida, et al., 2013, Soft Matter 9 (3), 811-9.