A Bipodal-Tethered Porphyrin for Attachment to Silicon Surfaces in Studies of Molecular Information Storage

An approach for molecular information storage entails use of redox-active molecules attached to an electroactive surface. Understanding the structural features that give rise to robust molecular monolayers with high charge density is an essential objective. Toward this goal, a zinc-porphyrin bearing an all-carbon bipodal tether, 5-(1,6-heptadien-4-yl)-15-phenyl-10,20-di-p-tolylporphinatozinc(II), has been synthesized by the reaction of a dipyrromethane and a dipyrromethane-1,9-dicarbinol. The porphyrin was attached to Si(100) via a high temperature procedure. The resulting molecular monolayers exhibited surface coverages, adsorption geometries, electron-transfer rates, and stabilities under repeated electrochemical cycling that are similar to those obtained with monopodal carbon tethers. The observation that the bipodal anchor does not provide enhanced stability is surprising given that attachment is achieved via two versus one covalent linkage.