Bottom-up fabrication of redox-active metal complex oligomer wires on an H-terminated Si(111) surface

Abstract

Linear and branched Fe(tpy)(2) complex oligomer wires were quantitatively formed on hydrogen-terminated silicon wafers by means of hydrosilylation of ethynylterpyridine and following stepwise coordination reactions, and the redox property of surface-attached species and its photosensitivity can be controlled by the doping density of the silicon wafers.

Surface‐Confined Heterometallic Molecular Dyads: Merging the Optical and Electronic Properties of Fe, Ru, and Os Terpyridyl Complexes

“…The high temporal, thermal, and photochemical stability, extraordinary electrochemical characteristics such as redox reversibility, low writing and erasing voltages, fast electron transfer rate, and charge holding capability for extended period (up to hours) make these materials suitable candidates for charge‐based data storage elements 3e, 5. In this context, homonuclear polypyridyl complex based monolayers and multilayers on metallic or insulating substrates have been prepared and extensively explored 2d, 3c, 5d, 6. However, to date, a little attention (with few exceptions)6e, 7 has been paid to the fabrication of heteronuclear polypyridyl complex based systems, even though they have lot of advantages as compared to the homonuclear constructs 3a, 6a, 7b, 8.…”

“…In this context, homonuclear polypyridyl complex based monolayers and multilayers on metallic or insulating substrates have been prepared and extensively explored 2d, 3c, 5d, 6. However, to date, a little attention (with few exceptions)6e, 7 has been paid to the fabrication of heteronuclear polypyridyl complex based systems, even though they have lot of advantages as compared to the homonuclear constructs 3a, 6a, 7b, 8. In particular, assemblies of more than one type of redox‐active components or coupling of hetero‐metallic segments offer multiple redox centers that can mediate multibit charge‐based data storage at molecular level.…”

Electron transport of bis(terpyridine)iron(II) complex wires on a semiconducting electrode

“…The asymmetric charge transfer and the photoresponsive redox behavior have been caused by the semiconducting electronic properties such as dopant type, resistivity and band gap [25][26][27][28][29][30][31][32].…”

Synthesis and Electron Transfer Properties of Metal Complex Oligomer Wires with an Inherent Potential Gradient on Gold Electrode

“…Coordination programming is, therefore, an important fundamental issue in the development of molecular electronics 1. We recently reported the construction of one‐ and three‐dimensional redox complex oligomer wires on gold,2–7 ITO,8, 9 and silicon surfaces 10. This method involved creating stepwise alternating connections between rigid bis‐ or tri‐(terpyridine) bridging ligands and octahedral metal ions to provide, respectively, linear or branched oligomer wires with a desired number and sequence of metal complex units 4, 10.…”

“…We recently reported the construction of one‐ and three‐dimensional redox complex oligomer wires on gold,2–7 ITO,8, 9 and silicon surfaces 10. This method involved creating stepwise alternating connections between rigid bis‐ or tri‐(terpyridine) bridging ligands and octahedral metal ions to provide, respectively, linear or branched oligomer wires with a desired number and sequence of metal complex units 4, 10. The electron transport mechanism and redox reaction kinetics of the films composed of linear and branched oligomer wires were examined, yielding the first observation of redox conduction through a single molecular wire in a redox polymer film 4.…”