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Hexadecaphyrin-( A Dual Site Ligand That Supports Thermal Conformational Changes

Anguera, Gonzalo, Cha, Won-Young, Moore, Matthew D., Lee, Juhoon, Guo, Shenyi, Lynch, Vincent M., Kim, Dongho, Sessler, Jonathan L.
Journal of the American Chemical Society 2018 v.140 no.11 pp. 4028-4034
cobalt, heat, ligands, macrocyclic compounds, oxidation, porphyrins, spectral analysis, zinc
A new expanded porphyrin, hexadecaphyrin-(, is reported. It was obtained via the condensation of a hexapyrrolic derivative prepared in turn from a bipyrrole dialdehyde and a stable quaterpyrrole precursor. This hexadecaphyrin contains eight direct α-pyrrole-to-α-pyrrole linkages in its structure. It supports the formation of bimetallic complexes of both zinc and cobalt that are characterized by different conformational structures. Furthermore, a mixed zinc/cobalt macrocycle has been prepared. The cobalt bimetallic complex shows two stable conformations with the same oxidation state that are in equilibrium. All compounds have been characterized by common spectroscopic means, and single crystal X-ray diffraction structures were obtained for all macrocyclic compounds. DFT calculations and transient absorption spectra were used to study the electronic features of the complexes and the effect of conformational changes. This system shows promise as an accumulated heat sensor.