title: Dicopper(II) metallacyclophanes as multifunctional magnetic devices: a joint experimental and computational study.
abstract: Metallosupramolecular complexes constitute an important advance in the emerging fields of molecular spintronics and quantum computation and a useful platform in the development of active components of spintronic circuits and quantum computers for applications in information processing and storage. The external control of chemical reactivity (electro- and photochemical) and physical properties (electronic and magnetic) in metallosupramolecular complexes is a current challenge in supramolecular coordination chemistry, which lies at the interface of several other supramolecular disciplines, including electro-, photo-, and magnetochemistry. The specific control of current flow or spin delocalization through a molecular assembly in response to one or many input signals leads to the concept of developing a molecule-based spintronics that can be viewed as a potential alternative to the classical molecule-based electronics. A great variety of factors can influence over these electronically or magnetically coupled, metallosupramolecular complexes in a reversible manner, electronic or photonic external stimuli being the most promising ones. The response ability of the metal centers and/or the organic bridging ligands to the application of an electric field or light irradiation, together with the geometrical features that allow the precise positioning in space of substituent groups, make these metal-organic systems particularly suitable to build highly integrated molecular spintronic circuits. In this Account, we describe the chemistry and physics of dinuclear copper(II) metallacyclophanes with oxamato-containing dinucleating ligands featuring redox- and photoactive aromatic spacers. Our recent works on dicopper(II) metallacyclophanes and earlier ones on related organic cyclophanes are now compared in a critical manner. Special focus is placed on the ligand design as well as in the combination of experimental and computational methods to demonstrate the multifunctionality nature of these metallosupramolecular complexes. This new class of oxamato-based dicopper(II) metallacyclophanes affords an excellent synthetic and theoretical set of models for both chemical and physical fundamental studies on redox- and photo-triggered, long-distance electron exchange phenomena, which are two major topics in molecular magnetism and molecular electronics. Apart from their use as ground tests for the fundamental research on the relative importance of the spin delocalization and spin polarization mechanisms of the electron exchange interaction through extended π-conjugated aromatic ligands in polymetallic complexes, oxamato-based dicopper(II) metallacyclophanes possessing spin-containing electro- and chromophores at the metal and/or the ligand counterparts emerge as potentially active (magnetic and electronic) molecular components to build a metal-based spintronic circuit. They are thus unique examples of multifunctional magnetic complexes to get single-molecule spintronic devices by controlling and allowing the spin communication, when serving as molecular magnetic couplers and wires, or by exhibiting bistable spin behavior, when acting as molecular magnetic rectifiers and switches. Oxamato-based dicopper(II) metallacyclophanes also emerge as potential candidates for the study of coherent electron transport through single molecules, both experimentally and theoretically. The results presented herein, which are a first step in the metallosupramolecular approach to molecular spintronics, intend to attract the attention of physicists and materials scientists with a large expertice in the manipulation and measurement of single-molecule electron transport properties, as well as in the processing and addressing of molecules on different supports.
authors.affiliation: †Institut de Ciència Molecular (ICMol), Universitat de Valencia, 46980 Paterna, València, Spain.
authors.forename: María
authors.initials: M
authors.lastname: Castellano
authors.affiliation: †Institut de Ciència Molecular (ICMol), Universitat de Valencia, 46980 Paterna, València, Spain.|‡Fundació General de la Universitat de València (FGUV), 46010 Valéncia, Spain.
authors.forename: Rafael
authors.initials: R
authors.lastname: Ruiz-García
authors.affiliation: †Institut de Ciència Molecular (ICMol), Universitat de Valencia, 46980 Paterna, València, Spain.|‡Fundació General de la Universitat de València (FGUV), 46010 Valéncia, Spain.
authors.forename: Joan
authors.initials: J
authors.lastname: Cano
authors.affiliation: †Institut de Ciència Molecular (ICMol), Universitat de Valencia, 46980 Paterna, València, Spain.
authors.forename: Jesús
authors.initials: J
authors.lastname: Ferrando-Soria
authors.affiliation: †Institut de Ciència Molecular (ICMol), Universitat de Valencia, 46980 Paterna, València, Spain.
authors.forename: Emilio
authors.initials: E
authors.lastname: Pardo
authors.affiliation: †Institut de Ciència Molecular (ICMol), Universitat de Valencia, 46980 Paterna, València, Spain.
authors.forename: Francisco R
authors.initials: FR
authors.lastname: Fortea-Pérez
authors.affiliation: †Institut de Ciència Molecular (ICMol), Universitat de Valencia, 46980 Paterna, València, Spain.
authors.forename: Salah-Eddine
authors.initials: SE
authors.lastname: Stiriba
authors.affiliation: †Institut de Ciència Molecular (ICMol), Universitat de Valencia, 46980 Paterna, València, Spain.
authors.forename: Miguel
authors.initials: M
authors.lastname: Julve
authors.affiliation: †Institut de Ciència Molecular (ICMol), Universitat de Valencia, 46980 Paterna, València, Spain.
authors.forename: Francesc
authors.initials: F
authors.lastname: Lloret