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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.

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Figure 1: Key characteristics of porphyrins and their control at surfaces.
Figure 2: Conformational adaptation, electronic and magnetic features of surface-confined tetrapyrroles.
Figure 3: Molecular rotation and switching, spin and electronic manipulation, ligation of adducts and metallation.
Figure 4: Supramolecular design with meso-substituted tetrapyrrole tectons at well-defined metal surfaces.
Figure 5: Formation of covalent nanostructures.
Figure 6: Organization of tetrapyrrole tectons at sp2-bonded sheet layers.
Figure 7: Porphyrinic hybrid architectures.
Figure 8: Bio-inspired interfacial tetrapyrrole nanosystems.

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Acknowledgements

We are grateful for support from the European Research Council Advanced Grant MolArt (no. 247299), the Munich Centre for Advanced Photonics (MAP) and TUM Institute for Advanced Study funded by the German Research Foundation (DFG) via the German Excellence Initiative, Canadian NSERC and CFI, the Spanish RyC Programme and other funding schemes. We thank all team members and project partners co-authoring cited joint publications.

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Auwärter, W., Écija, D., Klappenberger, F. et al. Porphyrins at interfaces. Nature Chem 7, 105–120 (2015). https://doi.org/10.1038/nchem.2159

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