(a) Chemical reduction of TP to afford the radical-anions, (b) coordination of TP– with K+, Rb+, and Cs+ ions. From Z. Zhou and M.A. Petrukhin, Coordination Chemistry Reviews 486 (2023) 215144. © 2023 Elsevier B.V. All rights reserved.

Planar and curved polycyclic aromatic hydrocarbons (PAHs) can serve as molecular models for a wide range of applications including fullerenes, carbon nanotubes, and graphene. This applicability has aroused a significant level of research into chemical reactivity and materials applications of designed nanocarbon 𝞹-systems as advanced anode materials in energy storage. But bringing these exciting potentialities to fruition has been hampered by the lack of information about direct structure–property cor- relations in these complex hybrid systems.

The authors of this study (which was published in the special issue of Coordination Chemistry Reviews, “The Female Stars of Coordination Chemistry”) opted to concentrate their research on the alkali-metal-induced reduction of selected PAHs in order to observe original metal binding and intercalation trends, site-specific coordination, and distinct carbon framework responses to stepwise electron uptake. This study was carried out at the Advanced Crystallography facility of NSF’s ChemMatCARS at Sector 15 of the Advanced Photon Source, Argonne National Laboratory.

Their work reveals a number of heretofore unknowns. Among them: 1) The prominent effect of carbon framework topology and interesting metal binding trends along with individual structural responses of 𝞹-systems to the addition of multiple electrons. 2) The alkali metal ion coordination in planar graphene fragments depends on the PAH surface size and symmetry and can be modulated with the help of secondary ligands. 3) Chemical reduction opens entirely an different coordination chemistry for bent, warped, and twisted molecular nanographenes with multiple internal and external sites as well as unique site-specific metal intercalation coupled with distinct framework responses.

These discoveries promise to spur future applications as advanced functional materials for energy storage and transport. In addition, applying these results to novel contorted nanocarbon systems with original framework topologies and hybrid and multi- layered structures promises to open new avenues for coordination chemistry and a wealth of practical applications.

See: Zheng Zhoua,b and Marina A. Petrukhina,b*,”Planar, curved and twisted molecular nanographenes: Reduction-induced alkali metal coordination,” Coordination Chemistry Reviews 486 (2023) 215144. aTongji University bUniversity at Albany *Correspondence: mpetrukhina@albany.edu DOI: 10.1016/j.ccr.2023.2151440010-8545 © 2023 Elsevier B.V. All rights reserved.

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