Self-assembly of tetraalkoxydinaphthophenazines in monolayers on HOPG by scanning tunneling microscopy

2D supramolecular organization in monolayers of tetraalkoxydinaphthophenazines, a new group of solution processable organic semiconductors obtained by simple functionalization of indanthrone (6,15-dihydrodinaphtho[2,3-a:2′,3′-h]phenazine-5,9,14,18-tetraone), an old intractable dye, was investigated by scanning tunneling microscopy (STM). Five derivatives with increasing substituent length from butoxy (P-C4) to dodecyloxy (P-C12) were tested. All derivatives show a strong tendency to form ordered monolayers on HOPG graphite via self-assembly which constitute of rows of molecules oriented in one direction. However, local arrangement in this 2D supramolecular organization is strongly dependent on the substituent length. Two tendencies in the structural evolution are observed. For butoxy (P-C4), hexyloxy (P-C6) and octyloxy (P-C8) derivatives increasing substituent length results in the transformation of the structure governed by the conjugated core interactions to the one in which mutual interactions of the alkoxy groups dominate. As a consequence, for P-C8 a very stable 2D structure is obtained with a nearly rectangular 2D unit cell, as a consequence of the alkoxy group interdigitation in two perpendicular directions. With further increase of the substituent length to decyloxy (P-C10) and dodecyloxy (P-C12) a different effect is observed—a directional expansion of the unit cell along the longitudinal axis of the molecules. This is a consequence of structural nonequivalence of the alkoxy groups attached to the same aromatic ring. [Display omitted] •2D organization of alkoxy derivatives of dinaphthophenazines on HOPG is reported.•STM contrast dependence on tip polarity is correlated with molecular orbitals.•2D structural evolution caused by alkoxy substituent length is analyzed.•Correlation between molecular orientation in adlayer and HOPG substrate is noted.