Pi-Extended Ethynyl 21,23-Dithiaporphyrins: A Synthesis and Comparative Study of Electrochemical, Optical, and Self-Assembling Properties

• Published in: Journal of organic chemistry 2015-10, Vol.80 (19), p.9401-9409
• Main Authors: Bromby, Ashley D, Keller, Samantha N, Bozek, Kevin J. A, Williams, Vance E, Sutherland, Todd C
• Format: Article
• Language: English
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/acs.joc.5b01299

21,23-Dithiaporphyrins were synthesized containing pi-extending ethynyl substituents at the meso positions. These porphyrins displayed highly bathochromic and broadened absorbance profiles spanning 400–900 nm with molar absorptivities ranging from 2500 to 300,000 M–1 cm–1. Electrochemically, these ethynyl dithiaporphyrins undergo a single oxidation at 0.44 or 0.57 V and reduction at −1.17 or −1.08 V versus a ferrocene/ferrocenium internal standard depending on the type of functionalization appended to the ethynyl group. DFT calculations predict that the delocalization of the frontier molecular orbitals should expand onto the meso positions of the ethynyl 21,23-dithiaporphyrins; shrinking the HOMO–LUMO energy gap by destabilizing the HOMO energy. Indeed, the DFT results agree with our optical and electrochemical assessments. Finally, differential scanning calorimetry combined with cross-polarized optical microscopy and powder X-ray diffraction was used to assess the ability of these porphyrins for long-range order. For the ethynylphenyl alkoxy 21,23-dithiaporphyin, birefringent, soft-crystalline-like domains were observed by polarized microscopy, which are marginally sustained by a low-level of crystallinity detected in the XRD, suggesting that long-range ordering is possible. Overall, ethynyl 21,23-dithiaporphyrins are able to harvest much lower energy light and possess lower oxidation and reduction potentials compared to their pyrrolic analogues, which are desirable properties for applications in organic electronics.