2024-03-28T09:46:05Zhttp://digital.csic.es/dspace-oai/requestoai:digital.csic.es:10261/1886992022-05-18T10:36:09Zcom_10261_89com_10261_3col_10261_342
Cirera, Borja
Trukhina, Olga
Björk, Jonas
Bottari, Giovanni
Rodríguez-Fernández, Jonathan
Martín-Jiménez, Alberto
Islyaikin, Mikhail K.
Otero, Roberto
Gallego, José M.
Miranda, R.
Torres, Tomás
Écija, David
2019-08-21T08:59:56Z
2019-08-21T08:59:56Z
2017-10-11
Journal of the American Chemical Society 139(40): 14129-14136 (2017)
http://hdl.handle.net/10261/188699
10.1021/jacs.7b06406
http://dx.doi.org/10.13039/100012818
http://dx.doi.org/10.13039/501100003329
http://dx.doi.org/10.13039/501100006769
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.
eng
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Long-Range Orientational Self-Assembly, Spatially Controlled Deprotonation, and Off-Centered Metalation of an Expanded Porphyrin
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