Izabela Schmidt

Application of 2-ethylpyrrole for a direct synthesis of 3-substituted inverted porphyrins

Abstract 3-Ethyl-5,10,15,20-tetraphenyl-2-aza-21-carbaporphyrin is the major macrocyclic product in the condensation of 2-ethylpyrrole, pyrrole, and benzaldehyde. Oxidation of the ethyl substituent leads to 3-(1′-hydroxyethyl)- and 3-acetyl-substituted inverted porphyrins.

An inverted porphyrin with a pendant pyrrole—identification of a tetraphenylsapphyrin isomer in the Rothemund synthesis

Abstract 2-Aza-3-(2′-pyrrolyl)-5,10,15,20-tetraphenyl-21-carbaporphyrin was identified among the products of a Rothemund synthesis and characterized. An alternative convenient method of its synthesis starting from 2-aza-5,10,15,20-tetraphenyl-21-carbaporphyrin was proposed.

Synthesis and photophysical characterization of porphyrin, chlorin and bacteriochlorin molecules bearing tethers for surface attachment.

The ability to tailor synthetic porphyrin, chlorin and bacteriochlorin molecules holds promise for diverse studies in artificial photosynthesis. Toward this goal, the synthesis and photophysical characterization of five tetrapyrrole compounds is described. Each compound bears a surface attachment group. One set contains three meso‐substituted porphyrins that differ only in the nature of a surface‐binding tether—isophthalic acid, ethynylisophthalic acid or cyanoacrylic acid. The other set includes a porphyrin, chlorin and bacteriochlorin each of which bears an ethynylisophthalic acid tether. The ester derivative of each compound was prepared for solution photophysical characterization studies. The photophysical studies include determination (in toluene or acetonitrile) of the electronic absorption and fluorescence spectra, fluorescence yield and lifetime of the lowest excited singlet state. The excited‐state lifetimes range from 1 to 5.6 ns for the five compounds. The radiative rate constant for the excited‐state decay was estimated from the photophysical data (fluorescence yield and excited‐state lifetime) and from Strickler–Berg analysis of the absorption and fluorescence spectra. The synthesis and characterization of the tetrapyrrole compounds underpin their use as sensitizers in molecular‐based solar cells.

Metal−Molecule Interactions Upon Deposition of Copper Overlayers on Reactively Functionalized Porphyrin Monolayers on Si(100)

The interaction of evaporated Cu deposited on a series of porphyrins in monolayers covalently attached to Si(100) substrates was investigated using cyclic voltammetry and FTIR spectroscopy. Each porphyrin contains a triallyl tripod attached to the porphyrin via a p-phenylene unit. The tripod anchors the porphyrin to the Si(100) substrate via hydrosilylation of the allyl groups. Two of the porphyrins are Zn chelates that possess meso p-cyanophenyl substituentsone, ZnP-CND, contains a single group opposite (distal) to the tripodal surface anchor, whereas the other, ZnP-CNL, contains two groups orthogonal (lateral) to the surface anchor. A third Zn porphyrin, ZnP, containing nonreactive p-tolyl groups at all three nonanchoring meso positions, was examined for comparison. The fourth porphyrin, FbP-HD, is a metal-free species (free base) that contains nonreactive phenyl (distal) and p-tolyl groups (lateral) at the three nonanchoring meso positions. The fifth porphyrin, CuP-HD, is the Cu chelate of FbP-HD, and serves as a reference complex for evaluating the effects of Cu metal deposition onto FbP-HD. The studies indicate that all of the porphyrin monolayers are robust under the conditions of Cu deposition, experiencing no noticeable degradation. In addition, the Cu metal does not penetrate through the monolayer to form electrically conductive filaments. For the ZnP-CND monolayers, the deposited Cu quantitatively reacts/complexes with the distal cyano group. In contrast, for the ZnP-CNL monolayers no reaction/complexation of the lateral cyano groups is observed. For the FbP-HD monolayers, Cu deposition results in quantitative insertion of Cu into the free base porphyrin. Collectively, the studies demonstrate that porphyrin monolayers are amenable to direct deposition of Cu overlayers and that functionalization of the porphyrins can be used to mediate the attributes of the metal-molecule junction.

Diverse porphyrin dimers as candidates for high-density charge-storage molecules

Porphyrinic molecules have been shown to be viable candidates for a molecular-based information storage medium on the basis of redox activity. An optimal redox-based information storage medium requires a large charge density in the molecular footprint on the anchoring substrate. The use of dimeric versus monomeric architectures affords one route to achieving increased charge density without sacrificing surface cross sectional area. Towards this goal, a series of zinc and cobalt containing porphyrin dimers has been prepared and characterized. The interporphyrin linkages in the dimers include p-phenylene, ethynyl, 1,4-butadiynyl, and ethynylphenylethynyl joining porphyrin meso-positions; Crossley-type fusion bridging porphyrin β-positions, and Osuka-type triple fusions bridging one meso- and two β-positions. The electrochemical features of each dimer have been evaluated.

Comparison of Electron-Transfer Rates for Metal- versus Ring-Centered Redox Processes of Porphyrins in Monolayers on Au(111)

The standard electron-transfer rate constants ( k ( 0 )) are measured for redox processes of Fe versus Zn porphyrins in monolayers on Au(111); the former undergoes a metal-centered redox process (conversion between Fe (III) and Fe (II) oxidation states) whereas the latter undergoes a ring-centered redox process (conversion between the neutral porphyrin and the pi-cation radical). Each porphyrin contains three meso-mesityl groups and a benzyl thiol for surface attachment. Under identical solvent (propylene carbonate)/electrolyte (1.0 M Bu 4NCl) conditions, the Zn (II) center has a coordinated Cl (-) ion when the porphyrin is in either the neutral or oxidized state. In the case of the Fe porphyrin, two species are observed a low-potential form ( E l (0) approximately -0.6 V) wherein the metal center has a coordinated Cl (-) ion when it is in either the Fe (II) or Fe (III) state and a high-potential form ( E h (0) approximately +0.2 V) wherein the metal center undergoes ligand exchange upon conversion from the Fe (III) to Fe (II) states. The k ( 0 ) values observed for all of the porphyrins depend on surface concentration, with higher concentrations resulting in slower rates, consistent with previous studies on porphyrin monolayers. The k ( 0 ) values for the ring-centered redox process (Zn chelate) are 10-40 times larger than those for the metal-centered process (Fe chelate); the k ( 0 ) values for the two forms of the Fe porphyrin differ by a factor of 2-4 (depending on surface concentration), the Cl (-) exchanging form generally exhibiting a faster rate. The faster rates for the ring- versus metal-centered redox process are attributed to the participating molecular orbitals and their proximity to the surface (given that the porphyrins are relatively upright on the surface): a pi molecular orbital that has significant electron density at the meso-carbon atoms (one of which is the site of attachment of the linker to the surface anchoring thiol) versus a d-orbital that is relatively well localized on the metal center.

Synthesis of porphyrins for metal deposition studies in molecular information storage applications

Porphyrins may serve as the active charge-storage medium in memory chips. A series of 14 porphyrins (trans-A2B2, trans-AB2C, or A4 type; free base, copper or zinc chelate) has been synthesized for investigation of metal deposition on porphyrin monolayers. Each trans-AB2C porphyrin is equipped with a surface attachment group and a distal functional group (or flanking functional groups). The surface attachment groups include S-acetylthiomethyl, hydroxymethyl, TMS-ethynyl, allyl, and triallylmethyl; the functional groups include amino, cyano, dipyrrin-5-yl, formyl, and nitro; all of which are attached to the p-position of a porphyrin meso-phenyl group. Two non-redox-active triallylmethyl-substituted arenes were also prepared for use as control compounds.