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