3 years ago

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

Long-Range Orientational Self-Assembly, Spatially Controlled Deprotonation, and Off-Centered Metalation of an Expanded Porphyrin
David Ecija, Tomás Torres, José M. Gallego, Alberto Martin-Jimenez, Giovanni Bottari, Roberto Otero, Borja Cirera, Mikhail K. Islyaikin, Jonathan Rodríguez-Fernández, Rodolfo Miranda, Jonas Björk, Olga Trukhina
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.

Publisher URL: http://dx.doi.org/10.1021/jacs.7b06406

DOI: 10.1021/jacs.7b06406

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