A new molecular nanographene, adamanphene, has been designed and synthesized by integrating an adamantane core with four peripheral hexa‐ peri ‐hexabenzocoronene (HBC) units, thus combining structural motifs reminiscent of two carbon allotropes, diamond (3D) and graphene (2D). The synthetic route enables the construction of this hybrid architecture with full control over the spatial arrangement of the HBC fragments. Single‐crystal X‐ray diffraction confirms a rigid tetrahedral framework that assembles into an open, highly porous packing supported by intermolecular π – π interactions. The electrochemical behavior of adamanphene reveals features of electronically decoupled HBC chromophores, while spectroscopic studies show absorption and emission profiles closely related to those of reference HBC derivatives. Notably, adamanphene exhibits distinct fluorescence behavior in solution and in the aggregated state, displaying a clear change in the color and shape of the emission upon increasing the proportion of poorly solubilizing solvent (e.g., water). TD‐DFT calculations reproduce the main experimental features and provide insight into the nature of the electronic transitions involved. The combination of a three‐dimensional sp 3 carbon core with multiple extended sp 2 π ‐surfaces defines adamanphene as a unique molecular platform for exploring the interplay between dimensionality, supramolecular organization, and photophysical response in carbon‐based nanostructures.
Iglesias‐Rabadán et al. (Sun,) studied this question.
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