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  • Induced magnetic field in s...
    Charistos, Nickolas D; Muñoz-Castro, Alvaro

    Physical chemistry chemical physics : PCCP, 05/2020, Letnik: 22, Številka: 17
    Journal Article

    The induced magnetic field of C 2 N ( N = 3-14) carbon rings was dissected to contributions from out-of-plane and in-plane π orbitals revealing two concurrent long range shielding or deshielding cones as a manifestation of the dual aromatic and antiaromatic character of C 4 n +2 and of C 4 n rings respectively. Aromaticity based on the magnetic criterion was evaluated with regard to the bonding pattern and geometrical characteristics that elucidate the influence of bond length and bond angle alteration on out-of-plane and in-plane magnetic responses. Ground state polyynic geometries of C 4 n +2 rings exhibit comparable shielding cones to annulenes, decreasing the magnetic response with regard to the ring size and similar π out and π in diatropicity. Transition state cumulenic rings display increased aromaticity expressed by a very strong constant magnetic response and augmented π out diatropicity with regard to π in . The variations of the induced magnetic field are explained on the basis of frontier orbital interactions through rotational excitations, which enable further rationalization of the aromatic/antiaromatic behavior. Two orthogonal sets of π orbitals induce concurrent (de)shielding cones demonstrating the double (anti)aromaticity of sp-hybridized carbon rings.