No abstract

A general method has been developed for the immobilization of metalloporphyrins at a gold electrode surface coated with a self-assembled monolayer (SAM). SAMs containing imidazole-terminated adsorbates are shown to bind a series of metalloporphyrins, including bis-acetonitrile octaethylporphyrinatoruthenium(II), Ru(OEP)(CH 3 CN) 2 ; bis-acetonitrile octaethyltetraazaporphyrinato ruthenium(II), Ru(OETAP)(CH 3 CN) 2 ; bisacetonitrile tetra-(p-chlorophenyl)porphyrinatoruthenium(II), Ru(Tp-ClPP)(CH 3 CN) 2 ; bis-acetonitrile octaethylporphyrinatoosmium(II), Os(OEP)(CH 3 CN) 2 ; and carbonyl meso-tetramesitylporphyrinatoruthenium(II), Ru(TMP)(CO). The SAM/metalloporphyrin films have been characterized by optical ellipsometry, contact angle goniometry, X-ray photoelectron spectroscopy, grazing angle FT-IR spectroscopy, transmission visible spectroscopy, and electrochemistry. The results indicate that the metalloporphyrins are chemisorbed via axial ligand substitution of the metal center with the porphyrin ring parallel to the surface and the second axial ligand position normal to the surface. Scanning tunneling microscopy images of Ru(TMP)(CO) bound to the SAM corroborate this model. Axial ligation of metalloporphyrins to SAMs serves as the basis for an iterative, defined approach to the preparation of stacked single component and mixed metalloporphyrin multilayers on SAMs. In these materials, the bidentate ligand pyrazine serves as a bridge between successive metalloporphyrins in the stacks.

The standard heterogeneous electron-transfer rate constants (k(n)0) between substrate gold electrodes and the ferrocene redox couple attached to the electrode surface by variable lengths of substituted or unsubstituted oligophenyleneethynylene (OPE) bridges as constituents of mixed self-assembled monolayers were measured as a function of temperature. The distance dependences of the unsubstituted OPE standard rate constants and of the preexponential factors (An) obtained from an Arrhenius analysis of the unsubstituted OPE k(n)0 versus temperature data are not monotonic. This surprising result, together with the distance dependence of the substituted OPE preexponential factors, may be assessed in terms of the likely conformational variability of the OPE bridges (as a result of the low intrinsic barrier to rotation of the phenylene rings in these bridges) and the associated sensitivity of the rate of electron transfer (and, hence, the single-molecule conductance which may be estimated using An) through these bridges to the conformation of the bridge. Additionally, the measured standard rate constants were independent of the identity of the diluent component of the mixed monolayer, and using an unsaturated OPE diluent has no effect on the rate of electron transfer through a long-chain alkanethiol bridge. These observations indicate that the diluent does not participate in the electron-transfer event.