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Cirera B, Trukhina O, Björk J, et al. Long-Range Orientational Self-Assembly, Spatially Controlled Deprotonation, and Off-Centered Metalation of an Expanded Porphyrin. J Am Chem Soc. 2017;139(40):14129-14136doi: 10.1021/jacs.7b06406.
Cirera, B., Trukhina, O., Björk, J., Bottari, G., Rodríguez-Fernández, J., Martin-Jimenez, A., Islyaikin, M. K., Otero, R., Gallego, J. M., Miranda, R., Torres, T., & Ecija, D. (2017). Long-Range Orientational Self-Assembly, Spatially Controlled Deprotonation, and Off-Centered Metalation of an Expanded Porphyrin. Journal of the American Chemical Society, 139(40), 14129-14136. https://doi.org/10.1021/jacs.7b06406
Cirera, Borja, et al. "Long-Range Orientational Self-Assembly, Spatially Controlled Deprotonation, and Off-Centered Metalation of an Expanded Porphyrin." Journal of the American Chemical Society vol. 139,40 (2017): 14129-14136. doi: https://doi.org/10.1021/jacs.7b06406
Cirera B, Trukhina O, Björk J, Bottari G, Rodríguez-Fernández J, Martin-Jimenez A, Islyaikin MK, Otero R, Gallego JM, Miranda R, Torres T, Ecija D. Long-Range Orientational Self-Assembly, Spatially Controlled Deprotonation, and Off-Centered Metalation of an Expanded Porphyrin. J Am Chem Soc. 2017 Oct 11;139(40):14129-14136. doi: 10.1021/jacs.7b06406. Epub 2017 Sep 27. PMID: 28889740.
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J Am Chem Soc. 2017 Oct 11;139(40):14129-14136. doi: 10.1021/jacs.7b06406. Epub 2017 Sep 27.

Long-Range Orientational Self-Assembly, Spatially Controlled Deprotonation, and Off-Centered Metalation of an Expanded Porphyrin.

Journal of the American Chemical Society

Borja Cirera, Olga Trukhina, Jonas Björk, Giovanni Bottari, Jonathan Rodríguez-Fernández, Alberto Martin-Jimenez, Mikhail K Islyaikin, Roberto Otero, José M Gallego, Rodolfo Miranda, Tomás Torres, David Ecija

Affiliations

  1. IMDEA Nanoscience , 28049 Madrid, Spain.
  2. Department of Organic Chemistry, Universidad Autónoma de Madrid , 28049 Madrid, Spain.
  3. Department of Physics, Chemistry and Biology, IFM, Linköping University , 58183 Linköping, Sweden.
  4. Institute for Advanced Research in Chemical Sciences (IAdChem), Universidad Autónoma de Madrid , 28049 Madrid, Spain.
  5. Department of Condensed Matter Physics, Universidad Autónoma de Madrid , 28049 Madrid, Spain.
  6. IRLoN, Research Institute of Macroheterocycles, Ivanovo State University of Chemistry and Technology , 153000 Ivanovo, Russia.
  7. Instituto de Ciencia de Materiales de Madrid, CSIC , 28049 Madrid, Spain.

PMID: 28889740 DOI: 10.1021/jacs.7b06406

Abstract

Expanded porphyrins are large-cavity macrocycles with enormous potential in coordination chemistry, anion sensing, photodynamic therapy, and optoelectronics. In the last two decades, the surface science community has assessed the physicochemical properties of tetrapyrrolic-like macrocycles. However, to date, the sublimation, self-assembly and atomistic insights of expanded porphyrins on surfaces have remained elusive. Here, we show the self-assembly on Au(111) of an expanded aza-porphyrin, namely, an "expanded hemiporphyrazine", through a unique growth mechanism based on long-range orientational self-assembly. Furthermore, a spatially controlled "writing" protocol on such self-assembled architecture is presented based on the STM tip-induced deprotonation of the inner protons of individual macrocycles. Finally, the capability of these surface-confined macrocycles to host lanthanide elements is assessed, introducing a novel off-centered coordination motif. The presented findings represent a milestone in the fields of porphyrinoid chemistry and surface science, revealing a great potential for novel surface patterning, opening new avenues for molecular level information storage, and boosting the emerging field of surface-confined coordination chemistry involving f-block elements.

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