title: Spin-Dependent Transport through Chiral Molecules Studied by Spin-Dependent Electrochemistry.
abstract: Molecular spintronics (spin + electronics), which aims to exploit both the spin degree of freedom and the electron charge in molecular devices, has recently received massive attention. Our recent experiments on molecular spintronics employ chiral molecules which have the unexpected property of acting as spin filters, by way of an effect we call "chiral-induced spin selectivity" (CISS). In this Account, we discuss new types of spin-dependent electrochemistry measurements and their use to probe the spin-dependent charge transport properties of nonmagnetic chiral conductive polymers and biomolecules, such as oligopeptides, L/D cysteine, cytochrome c, bacteriorhodopsin (bR), and oligopeptide-CdSe nanoparticles (NPs) hybrid structures. Spin-dependent electrochemical measurements were carried out by employing ferromagnetic electrodes modified with chiral molecules used as the working electrode. Redox probes were used either in solution or when directly attached to the ferromagnetic electrodes. During the electrochemical measurements, the ferromagnetic electrode was magnetized either with its magnetic moment pointing "UP" or "DOWN" using a permanent magnet (H = 0.5 T), placed underneath the chemically modified ferromagnetic electrodes. The spin polarization of the current was found to be in the range of 5-30%, even in the case of small chiral molecules. Chiral films of the l- and d-cysteine tethered with a redox-active dye, toludin blue O, show spin polarizarion that depends on the chirality. Because the nickel electrodes are susceptible to corrosion, we explored the effect of coating them with a thin gold overlayer. The effect of the gold layer on the spin polarization of the electrons ejected from the electrode was investigated. In addition, the role of the structure of the protein on the spin selective transport was also studied as a function of bias voltage and the effect of protein denaturation was revealed. In addition to "dark" measurements, we also describe photoelectrochemical measurements in which light is used to affect the spin selective electron transport through the chiral molecules. We describe how the excitation of a chromophore (such as CdSe nanoparticles), which is attached to a chiral working electrode, can flip the preferred spin orientation of the photocurrent, when measured under the identical conditions. Thus, chirality-induced spin polarization, when combined with light and magnetic field effects, opens new avenues for the study of the spin transport properties of chiral molecules and biomolecules and for creating new types of spintronic devices in which light and molecular chirality provide new functions and properties.
authors: Department of Chemical Physics, Weizmann Institute of Science , Rehovot 76100, Israel.
authors: Prakash Chandra
authors: PC
authors: Mondal
authors: Department of Chemical Physics, Weizmann Institute of Science , Rehovot 76100, Israel.|Department of Engineering, University of Modena and Reggio Emilia , Via Vivarelli 10, 41125 Modena, Italy.
authors: Claudio
authors: C
authors: Fontanesi
authors: Department of Chemistry, University of Pittsburgh , Pittsburgh, Pennsylvania 15260, United States.
authors: David H
authors: DH
authors: Waldeck
authors: Department of Chemical Physics, Weizmann Institute of Science , Rehovot 76100, Israel.
authors: Ron
authors: R
authors: Naaman
mesh_terms: D001436:Bacteriorhodopsins / Q000737:chemistry; D002104:Cadmium / Q000737:chemistry; D003545:Cysteine / Q000737:chemistry; D045304:Cytochromes c / Q000737:chemistry; D055664:Electrochemical Techniques; D004566:Electrodes; D004583:Electrons; D006046:Gold / Q000737:chemistry; D060328:Magnetic Phenomena; D053758:Nanoparticles; D009532:Nickel / Q000737:chemistry; D009842:Oligopeptides / Q000737:chemistry; D010084:Oxidation-Reduction; D012643:Selenium / Q000737:chemistry; D013237:Stereoisomerism; D014048:Tolonium Chloride / Q000737:chemistry
chemical_list: D009842:Oligopeptides; D002104:Cadmium; D014048:Tolonium Chloride; D001436:Bacteriorhodopsins; D006046:Gold; D009532:Nickel; D045304:Cytochromes c; D012643:Selenium; D003545:Cysteine