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In 1966, Zimmerman proposed a type of Möbius aromaticity that involves through‐space electron delocalization; it has since been widely applied to explain reactivity in pericyclic reactions, but is considered to be limited to transition‐state structures. Although the easily accessible hexahelicene radical anion has been known for more than half a century, it was overlooked that it exhibits a ground‐state minimum and robust Zimmerman‐Möbius aromaticity in its central noose‐like opening, becoming, hence, the oldest existing Möbius aromatic system and with smallest Möbius cycle known. Despite its overall aromatic stabilization energy of 13.6 kcal mol−1 (at B3LYP/6‐311+G**), the radical also features a strong, globally induced paramagnetic ring current along its outer edge. Exclusive global paramagnetic currents can also be found in other fully delocalized radical anions of 4N+2 π‐electron aromatic polycyclic benzenoid hydrocarbons (PAH), thus questioning the established magnetic criterion of antiaromaticity. As an example of a PAH with nontrivial topology, we studied a novel Möbius[16]cyclacene that has a non‐orientable surface manifold and a stable closed‐shell singlet ground state at several density functional theory levels. Its metallic monoanion radical (0.0095 eV band gap at HSE06/6‐31G* level) is also wave‐function stable and displays an unusual 4π‐periodic, magnetically induced ring current (reminiscent of the transformation behaviour of spinors under spatial rotation), thus indicating the existence of a new, Hückel‐rule‐evading type of aromaticity. [ABSTRACT FROM AUTHOR]

Abstract: Magnetic aromaticity and antiaromaticity of closed shell metalloaromatics with 4d transition metals (Nb, Tc, Rh) is strictly correlated with the orbital topology (Möbius or Hückel) of their π‐HOMO, investigated computationally with DFT methods. A surprisingly simple rule emerged: the metallacycle is aromatic (antiaromatic) when the number of π MOs is even and the π‐HOMO is of Möbius (Hückel) topology‐and vice versa when the number of π MOs is odd. [ABSTRACT FROM AUTHOR]