Kannan Muthukumaran

Multiple-bit storage properties of porphyrin monolayers on SiO2

Hybrid molecule-silicon capacitors have been fabricated by the self-assembly of a monolayer of porphyrin molecules on a silicon oxide surface. The porphyrin employed [5-(4-dihydroxyphosphorylphenyl)-10,15,20-trimesitylporphinatozinc(II)] attaches to silicon oxide via a phosphonate linkage. Cyclic voltammetry current and capacitance/conductance measurements have been used to characterize the capacitors. The presence of multiple distinct peaks in current density and capacitance/conductance measurements are associated with oxidation and reduction of the molecular monolayer. The charge-storage states of the capacitor indicate applicability for use in multiple-bit memory devices.

Synthesis of dipyrrin-containing architectures

Dipyrrins are valuable precursors to dyes [dipyrrinatoboron difluoride, bis(dipyrrinato)-zinc(II) complexes] and serve as ligands in a variety of self-assembled materials. Six new dipyrrin-containing architectures have been synthesized. The architectures include bis(dipyrrinato) complexes containing copper(II) or palladium(II), a dipyrrin bearing a protected phosphonic acid unit, a porphyrin bearing two dipyrrins in a trans configuration, a linear diphenylethyne-linked dipyrromethane-dipyrrin building block, and a triad composed of two zinc porphyrins joined via an intervening bis(dipyrrinato)copper(II) complex. Two porphodimethenatozinc complexes were prepared and found to have Φf ≤ 0.002 (in toluene at room temperature), which is substantially less than the analogous bis(dipyrrinato)zinc complexes. Taken together, the syntheses described herein should broaden access to dipyrrins for use as complexation motifs in supramolecular chemistry and as pigments in light-harvesting applications.