Structure and Conformation of Individual Molecules upon Adsorption of a Mixture of Benzoporphyrins on Ag(111), Cu(111), and Cu(110) Surfaces.

We investigated the adsorption behavior of a mixture of six 2H-tetrakis-(3, 5-di-tert-butylphenyl)(x)benzoporphyrins (2H-diTTBP(x)BPs, x=0, 1, 2-cis, 2-trans, 3, and 4) on Ag(111), Cu(111) and Cu(110) at room temperature by scanning tunneling microscopy (STM) under ultra-high vacuum conditions. On Ag(111), we observe an ordered two-dimensional square phase, which is stable up to 400 K. On Cu(111), the same square phase coexists with a stripe phase, which disappears at 400 K. In contrast, on Cu(110), 2H-diTTBP(x)BPs adsorb as immobile isolated molecules or dispersed short chains along the [1 0] substrate direction, which remain intact up to 450 K. The stabilization of the 2D supramolecular structures on Ag(111) and Cu(111), and of the 1D short chains on Cu(110) is attributed to van der Waals interactions between the tert-butyl and phenyl groups of neighboring molecules. From high-resolution STM, we can assign all six 2H-diTTBP(x)BPs within the ordered structures. Moreover, we deduce a crown shape quadratic conformation on Ag(111) and Cu(111), an additional saddle-shape on Cu(111), and an inverted structure and a quadratic appearance on Cu(110). The different conformations are attributed to the different degree of interaction of the iminic nitrogen atoms of the isoindole and pyrrole groups with the substrate atoms.