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Spin–Spin Interactions in One‐Dimensional Assemblies of a Cumulene‐Based Singlet Biradical
Author(s) -
Hirao Yasukazu,
Daifuku Yoko,
Ihara Keiji,
Kubo Takashi
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202105740
Subject(s) - cumulene , singlet state , chemistry , intermolecular force , spin (aerodynamics) , raman spectroscopy , chemical physics , molecule , crystallography , photochemistry , molecular physics , atomic physics , physics , organic chemistry , excited state , optics , thermodynamics
The synthesis of phenalenyl‐endcapped [5]cumulene as a cumulene‐based singlet biradical and the spin correlation changes of one‐dimensional aggregates are described. The high propensity for self‐aggregation of phenalenyl rings and the introduction of bulky substituents into the appropriate positions led to the formation of a one‐dimensional chain assembly. Single‐crystal X‐ray structural analysis indicated that the bond length alternation of the cumulene chain increased with decreasing temperature, along with improved overlapping of the phenalenyl rings. Variable‐temperature Raman spectroscopy and magnetic susceptibility measurements revealed that a localized spin pair within the molecule decouples at low temperatures, and a continuum spin system involving intra‐ and intermolecular spin–spin interactions emerges in the one‐dimensional chain.