title: Porphyrins at interfaces.
abstract: Porphyrins and other tetrapyrrole macrocycles possess an impressive variety of functional properties that have been exploited in natural and artificial systems. Different metal centres incorporated within the tetradentate ligand are key for achieving and regulating vital processes, including reversible axial ligation of adducts, electron transfer, light-harvesting and catalytic transformations. Tailored substituents optimize their performance, dictating their arrangement in specific environments and mediating the assembly of molecular nanoarchitectures. Here we review the current understanding of these species at well-defined interfaces, disclosing exquisite insights into their structural and chemical properties, and also discussing methods by which to manipulate their intramolecular and organizational features. The distinct characteristics arising from the interfacial confinement offer intriguing prospects for molecular science and advanced materials. We assess the role of surface interactions with respect to electronic and physicochemical characteristics, and describe in situ metallation pathways, molecular magnetism, rotation and switching. The engineering of nanostructures, organized layers, interfacial hybrid and bio-inspired systems is also addressed.
authors.affiliation: Physik Department E20, TU München, James-Franck Strasse, D-85748 Garching, Germany.
authors.forename: Willi
authors.initials: W
authors.lastname: Auwärter
authors.affiliation: 1] Physik Department E20, TU München, James-Franck Strasse, D-85748 Garching, Germany [2] IMDEA Nanoscience, C/Faraday, 9, Campus Universitario de Cantoblanco, 28049 Madrid, Spain.
authors.forename: David
authors.initials: D
authors.lastname: Écija
authors.affiliation: Physik Department E20, TU München, James-Franck Strasse, D-85748 Garching, Germany.
authors.forename: Florian
authors.initials: F
authors.lastname: Klappenberger
authors.affiliation: Physik Department E20, TU München, James-Franck Strasse, D-85748 Garching, Germany.
authors.forename: Johannes V
authors.initials: JV
authors.lastname: Barth
mesh_terms: D004579:Electron Transport; D004583:Electrons; D008280:Magnetics; D049329:Nanostructures / Q000737:chemistry; D011166:Porphyrins / Q000737:chemistry*; D011789:Quantum Theory; D013499:Surface Properties
chemical_list: D011166:Porphyrins