We have prepared a series of four-coordinate metalloporphyrins (M(TPP), TPP is tetraphenylporphyrin and M(TPFPP), TPFPP is tetrapentafluorophenylpor-phyrin; M is Zn2+, Ni2+, Pt2+, or Pd2+) with distinct meso-substituents and their Magne-to-Optical Activity (MOA) was characterized by magnetic circular dichroism (MCD) and Magneto-Optical Rotary Dispersion spectroscopy (MORD; also known as Faraday Rotation spectroscopy). MORD spectra were calculated from the Kramers-Kronig relationship between MCD and MORD with the Hilbert transformation. The data show that the presence of the pentafluorophenyl group results in a significant increase in MOA in comparison to the phenyl group. The Gouterman four-orbital model is used to explain the MOA of these compounds.
This conference presentation, “New ligands and approaches to RSA materials” was presented at the Organic Photonic Materials and Devices XXIV conference at SPIE Photonics West 2022.
We have established that film morphology and laser induced heating from dye absorption are important parameters in the creation of new photonastic materials. Photonastic is defined as regular, repeatable movement in a pre-programmed direction following exposure to light. This work builds upon the development of photonastic polymers of ruthenium sulfoxide complexes, where the action of bending is ascribed to phototriggered isomerization of a sulfoxide ligand in a ruthenium coordination complex that is covalently attached to polynorbornene. The bending is analyzed in terms of a bilayer cantilever model.
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