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Herein, a hetero(S,N)‐quintuple [9]helicene (SNQ9H) molecule with an azacorannulene core was synthesized, currently representing the highest hetero‐helicene reported in the field of multiple [n]helicenes. X‐ray crystallography indicated that SNQ9H includes not only a propeller‐shaped conformer SNQ9H‐1, but also an unforeseen quasi‐propeller‐shaped conformer SNQ9H‐2. Different conformers were observed for the first time in multiple [n≥9]helicenes, likely owing to the doping of heteroatomic sulfurs in the helical skeletons. Remarkably, the ratio of SNQ9H‐1 to SNQ9H‐2 can be regulated in situ by the reaction temperature. Experimental studies on the photophysical and redox properties of SNQ9H and theoretical calculations clearly demonstrated that the electronic structures of SNQ9H depend on their molecular conformations. The strategy of introducing heteroatomic sulfurs into the helical skeleton may be useful in constructing various conformers of higher multiple [n]helicenes in the future. [ABSTRACT FROM AUTHOR]

Main observation and conclusion: Because of its unsaturated bonds, C60 is susceptible to polymerize into dimers. The implications of nitrogen doping on the geometrical and electronic structure of C60 dimers have been ambiguous for years. A quarter‐century after the discovery of azafullerene dimer (C59N)2, we reported its single crystallographic structure in 2019. Herein, the unambiguous crystal structure information of (C59N)2 is elucidated specifically, revealing that the inter‐cage C—C single bond length of (C59N)2 is comparable with that of an ordinary C(sp3)‐C(sp3) single bond, and that the most stable conformer of (C59N)2 is gauche‐conformer with a dihedral angle of 66°. To amend the structural deviations, geometrical structure of (C59N)2 is optimized by a B3LYP‐D3BJ function, which is proved to be more consistent with its single crystal structure than those by the commonly used B3LYP function. Moreover, the calculation method is also suitable for other representative fullerene dimers, such as (C60)2 and its divalent anion. Additionally, the dissociation of (C59N)2 at 473 K under mass spectrometric conditions suggests the inter‐cage C—C bond is relatively weaker than an ordinary C—C single bond, which can be explained by the interaction energies of inter‐cages. [ABSTRACT FROM AUTHOR]