High-Spin S = 3/2 Ground-State Aminyl Triradicals: Toward High-Spin Oligo-Aza Nanographenes
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High-spin ground-state polyradicals are an important platform due to their potential applications in magnetic and spintronic devices. However, a low high-to-low spin energy gap limits the population of the high-spin state, precluding their application at room temperature. Also, design strategies delineating control of the ground electronic state from a closed-shell low-spin to open-shell polyradical character with a high-spin ground state are not well established. Here, we report indacenodinaphthothiophene isomers fused with a 6,6-dicyanofulvene group showing a high-spin quintet ground state. Density functional theory calculations indicate that the syn - and anti -configurations have a closed-shell low-spin singlet ground state. However, the linear -configuration displays a high-spin quintet ground state, with the energy difference between the high-spin quintet to the nearest low-spin excited states calculated to be as large as 0.24 eV (≈5.60 kcal mol −1 ), exhibiting an exclusive population of the high-spin quintet state at room temperature. These molecules are compelling synthetic targets for use in magnetic and spintronic applications.more » « less
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null (Ed.)Abstract We lay the foundation for a version of $$r$$-spin theory in genus zero for Riemann surfaces with boundary. In particular, we define the notion of $$r$$-spin disks, their moduli space, and the Witten bundle; we show that the moduli space is a compact smooth orientable orbifold with corners, and we prove that the Witten bundle is canonically relatively oriented relative to the moduli space. In the sequel to this paper, we use these constructions to define open $$r$$-spin intersection theory and relate it to the Gelfand–Dickey hierarchy, thus providing an analog of Witten’s $$r$$-spin conjecture in the open setting.more » « less
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