Porphyrins as molecular electronic components of functional devices

Abstract

The proposal that molecules can perform electronic functions in devices such as diodes, rectifiers, wires, capacitors, or serve as functional materials for electronic or magnetic memory, has stimulated intense research across physics, chemistry, and engineering for over 35 years. Because biology uses porphyrins and metalloporphyrins as catalysts, small molecule transporters, electrical conduits, and energy transducers in photosynthesis, porphyrins are an obvious class of molecules to investigate for molecular electronic functions. Of the numerous kinds of molecules under investigation for molecular electronics applications, porphyrins and their related macrocycles are of particular interest because they are robust and their electronic properties can be tuned by chelation of a metal ion and substitution on the macrocycle. The other porphyrinoids have equally variable and adjustable photophysical properties, thus photonic applications are potentiated. At least in the near term, realistic architectures for molecular electronics will require self-organization or nanoprinting on surfaces. This review concentrates on self-organized porphyrinoids as components of working electronic devices on electronically active substrates with particular emphasis on the effect of surface, molecular design, molecular orientation and matrix on the detailed electronic properties of single molecules.

Self-assembly and coverage dependent thermally induced conformational changes of Ni(ii)-meso-tetrakis (4-tert-butylphenyl) benzoporphyrin on Cu(111)

“…7,[9][10][11] One important group of such organic molecules are porphyrins, which have numerous technological applications due to their versatile functionalities and distinct chemical and physical properties. 12,13 During the past few years, extensive attention has been paid to porphyrins self-assembled on metal surfaces in order to gain more information about their electronic properties, inherent conformational flexibility and reactivity. 4,[14][15][16][17][18][19][20][21][22][23][24][25][26][27] It has been demonstrated that the adsorption behaviour of porphyrins, such as intramolecular conformation and supramolecular arrangement, is strongly dependent on the actual substrate, 5,21,28 the coverage of these molecules, 22 the surface temperature 4,23,29 and the functional side groups of the porphyrin macrocycle.…”

Oxidation of Porphyrins in the Presence of Nucleophiles: From the Synthesis of Multisubstituted Porphyrins to the Electropolymerization of the Macrocycles

“…Indeed, in such systems, proteins are replaced by metalloporphyrins which can mimic the structure and/or the activity of the prosthetic groups of enzymes (Traylor, 1991). Another area of applications of such assembled porphyrins systems consists in the field of nanomaterials, the electronic communication between the macrocycles allowing developments of molecular photonic, electronic or optoelectronic devices (Jurow et al, 2010). Finally, nanocomposite porphyrins-based materials have also been investigated for applications involving energy storage systems, fuel cells and sensors (Di Natale et al, 2010;Ma et al, 2006).…”

Thermally induced anchoring of a zinc-carboxyphenylporphyrin on rutile TiO2 (110)

“…Both are crucial for molecular electronics, catalysis, and photovoltaics. [4][5][6][7][8][9] The properties of the molecule and their interaction with the surface can be tuned with functional chemical groups. Especially important are the so-called anchoring groups that show a strong adsorption to the substrate and are used for the immobilization of molecules on surfaces, which is essential for stable interfaces.…”