Synthesis of thiol-derivatized porphyrin dimers and trimers for studies of architectural effects on multibit information storage

Abstract

We present the rational design and synthesis of multiporphyrin arrays containing thiol-derivatized linkers for the purpose of multibit molecular information storage. Porphyrin dimers and trimers were synthesized by the Pd-mediated coupling of iodo-substituted and ethynyl-substituted porphyrin building blocks in 5-51% yields. Each porphyrin dimer bears one S-acetylthio group. The architecture of the trimers incorporates a trans-substituted porphyrin (central) bearing two S-acetylthio groups and two diphenylethyne-linked porphyrins (wings) in a trans geometry. The central porphyrin and the wing porphyrins bear distinct substituents and central metals, thereby affording different oxidation potentials. The S-acetylthio groups provide a means for attachment of the arrays to an electroactive surface. The dimers are designed for vertical orientation on an electroactive surface while the trimers are designed for horizontal orientation of the central porphyrin. Altogether seven different arrays were synthesized. Each array forms a self-assembled monolayer (SAM) on gold via in situ cleavage of the S-acetyl protecting group. The SAM of each array is electrochemically robust and exhibits multiple, reversible oxidation waves. In general, however, the trimeric arrays appear to form more highly ordered monolayers that exhibit sharper, better-defined redox features.