A hydrogen-bonded two-dimensionally networked buckybowl architecture is presented. Two types of hexagonal network (HexNet) structures (CPSM-1 and CPSM-2) have been achieved based on a sumanene derivative (CPSM) possessing 4,4'-dicarboxy-o-terphenyl groups in the periphery. CPSM-1 has a waved HexNet structure with an alternate alignment of upward and downward bowls. CPSM-2 has a bilayered HexNet structure composed of hamburger-shaped dimers of the bowls. This demonstrates that non-planar π-systems can be networked two-dimensionally by an appropriate supramolecular synthon to achieve structurally well-defined unique bumpy π-sheets. Furthermore, we revealed that CPSM-2 undergoes anisotropic shrinking along the c axis by 11 % under high pressure conditions (970 MPa). The shrinkage is brought about by offset sliding between bumpy π-surfaces of the bilayered HexNet sheets.

) 2, 3,5,6,8,9-hexabromosumanene (2) with Br groups at all the peripheral aromatic carbons was successfully synthesized. Single-crystal X-ray structural analysis of 2 revealed the formation of a one-dimensional columnar structure in the solid state, where the molecules overlapped in an eclipsed manner. The SuzukiMiyaura cross-coupling of 2 and various arylboronic acids gave hexaarylsumanene derivatives (3a3h) in good-to-moderate yields. The NMR spectroscopic analysis and theoretical calculations of 2 and hexaphenylsumanene (3a) revealed that the six peripheral functional groups do not significantly affect the original bowl structure or bowl-to-bowl inversion behavior of sumanene.

2,3,5,6,8,9-Hexakis(phenoxycarbonyl)sumanene, a hexa­substituted sumanene with CO2Ph groups at the peripheral aromatic carbons, was successfully prepared in good yield by Pd-catalyzed phenoxycarbonylation­ using a solvent of phenyl formate. Single-crystal X-ray structural analysis of this compound revealed the formation of a one-dimensional columnar structure, stacked in a staggered manner. The UV and emission spectra of this showed clear red-shifts compared with those of pristine sumanene, indicating the extension of the conjugation system.

Ah ydrogen-bonded two-dimensionally networked buckybowl architecture is presented. Twot ypes of hexagonal network (HexNet) structures (CPSM-1 and CPSM-2)h ave been achieved based on as umanene derivative (CPSM) possessing 4,4'-dicarboxy-o-terphenyl groups in the periphery. CPSM-1 has aw aved HexNet structure with an alternate alignment of upward and downward bowls. CPSM-2 has ab ilayered HexNet structure composed of hamburger-shaped dimers of the bowls.T his demonstrates that non-planar psystems can be networked two-dimensionally by an appropriate supramolecular synthon to achieve structurally welldefined unique bumpy p-sheets.F urthermore,w er evealed that CPSM-2 undergoes anisotropic shrinking along the caxis by 11 %u nder high pressure conditions (970 MPa). The shrinkage is brought about by offset sliding between bumpy p-surfaces of the bilayeredHexNet sheets.

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