Badía-Domínguez, Irene, Pérez-Guardiola, Andrés, Sancho-Garcia, Juan-Carlos, López Navarrete, Juan T., Hernández Jolín, Víctor, Li, Hongxiang, Sakamaki, Daisuke, Seki, Shu, Ruiz Delgado, M. Carmen
Formation of Cyclophane Macrocycles in Carbazole-Based Biradicaloids: Impact of the Dicyanomethylene Substitution Position
ACS Omega. 2019, 4(3): 4761-4769. doi:10.1021/acsomega.8b03418
URI: http://hdl.handle.net/10045/89307
DOI: 10.1021/acsomega.8b03418
ISSN: 2470-1343
Abstract: 
We have recently demonstrated that carbazole-based biradicaloids are promising building blocks in dynamic covalent chemistry. To elucidate their intriguing dynamic covalent chemical properties, it is necessary to understand the physical origin of their biradical nature. To this end, here we focus on two quinoid carbazole systems substituted with dicyanomethylene (DCM) groups via para (p-Cz-alkyl) or meta positions (m-Cz-ph), which are able to form cyclophane macrocycles by the formation of long C–C bonds between the bridgehead carbon atoms linked to the DCM groups. We aim at exploring the following questions: (i) How is the biradicaloid character of a quinoid carbazole affected by the substitution position of the DCM groups? (ii) How is the stability of the resulted cyclophane aggregate attained? (iii) How is the dynamic interconversion between the carbazole-based monomers and cyclophane aggregates affected by this subtle change in the substitution pattern position? Density functional theory-based calculations reveal that both p-Cz-alkyl and m-Cz-ph are open-shell biradicals in the ground electronic state, with the DCM substitution in the meta position resulting in a more pronounced biradical character. In contrast, the derivatization via the nitrogen of the carbazole unit is not predicted to affect the biradicaloid character. The spontaneous nature of the cyclophane-based macrocycle formation (i.e., the cyclic tetramer in p-Cz-alkyl and the cyclic trimer and the tetramer in m-Cz-ph) is supported by the negative relative Gibbs free energies calculated at 298 K. Interestingly, cyclic oligomers in which the DCM groups are inserted in the meta position tend to adopt folded conformations with attractive π–π interactions resulting in more stable aggregates; in contrast, note that an extended ring-shaped conformation is acquired for (p-Cz-alkyl)4. In addition, the larger spin density on the bridgehead carbon atom in the meta-substituted system strengthens the bridging C–C bond in the aggregate forms, hampering its dissociation. In fact, the C–C bond dissociation of (m-Cz-ph)4 and (m-Cz-ph)3 was suppressed in solution state, although it was achieved in solid state in response to soft external stimuli (i.e., temperature and grinding). In summary, we report a very comprehensive study aiming at elucidating the challenging chemical properties of carbazole-based biradicaloid systems.
Keywords:Cyclophane macrocycles, Carbazole-based biradicaloids, Dicyanomethylene substitution position
American Chemical Society
info:eu-repo/semantics/article