Spin Delocalization in the Radical Cations of Porphyrin Molecular Wires: A New Perspective on EPR Approaches.

ABSTRACT: The spin delocalization in the radical cations of a series of ethyne-linked oligoporphyrins was investigated using EPR spectroscopy. The room-temperature spectral envelope for these oligomers deviates significantly from the benchmark N^-0.5 trend in line width expected for a completely delocalized spin density, in contrast to the butadiyne-linked analogues measured previously. Here, we show, using DFT calculations and complementary low-temperature ENDOR measurements, that this deviation is primarily driven by a more pronounced inequivalence of the ¹⁴N spins within individual subunits for the ethyne-linked oligoporphyrins. Once this ¹⁴N inequivalence is taken into consideration, the room-temperature and ENDOR spectra for both butadiyne-linked and ethyne-linked oligomers, up to N = 5, can be simulated by similar static delocalization patterns. This work highlights the importance of EPR in exploring such spin delocalization phenomena while also demonstrating that the N^-0.5 trend should not be interpreted in isolation but only in combination with careful simulation and theoretical modeling.

SUBMITTER: Moise G 

PROVIDER: S-EPMC6778911 | biostudies-literature | 2019 Oct

REPOSITORIES: biostudies-literature