Thermally and Magnetically Robust Triplet Ground State Diradical

Nolan Gallagher, Hui Zhang, Tobias Junghoefer, Erika Giangrisostomi, Ruslan Ovsyannikov, Maren Pink, Suchada Rajca, Maria Benedetta Casu, Andrzej Rajca

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15 Scopus citations

Abstract

High spin (S = 1) organic diradicals may offer enhanced properties with respect to several emerging technologies, but typically exhibit low singlet triplet energy gaps and possess limited thermal stability. We report triplet ground state diradical 2 with a large singlet-triplet energy gap, Î"E ST ≥ 1.7 kcal mol -1 , leading to nearly exclusive population of triplet ground state at room temperature, and good thermal stability with onset of decomposition at â160 °C under inert atmosphere. Magnetic properties of 2 and the previously prepared diradical 1 are characterized by SQUID magnetometry of polycrystalline powders, in polystyrene glass, and in other matrices. Polycrystalline diradical 2 forms a novel one-dimensional (1D) spin-1 (S = 1) chain of organic radicals with intrachain antiferromagnetic coupling of J′/k = â14 K, which is associated with the N···N and N···O intermolecular contacts. The intrachain antiferromagnetic coupling in 2 is by far strongest among all studied 1D S = 1 chains of organic radicals, which also makes 1D S = 1 chains of 2 most isotropic, and therefore an excellent system for studies of low-dimensional magnetism. In polystyrene glass and in frozen benzene or dibutyl phthalate solution, both 1 and 2 are monomeric. Diradical 2 is thermally robust and is evaporated under ultrahigh vacuum to form thin films of intact diradicals on silicon substrate, as demonstrated by X-ray photoelectron spectroscopy. Based on C-K NEXAFS spectra and AFM images of the â1.5 nm thick films, the diradical molecules form islands on the substrate with molecules stacked approximately along the crystallographic a-axis. The films are stable under ultrahigh vacuum for at least 60 h but show signs of decomposition when exposed to ambient conditions for 7 h.

Original languageEnglish (US)
JournalJournal of the American Chemical Society
DOIs
StatePublished - Jan 1 2019

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ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Gallagher, N., Zhang, H., Junghoefer, T., Giangrisostomi, E., Ovsyannikov, R., Pink, M., Rajca, S., Casu, M. B., & Rajca, A. (2019). Thermally and Magnetically Robust Triplet Ground State Diradical. Journal of the American Chemical Society. https://doi.org/10.1021/jacs.9b00558