RT info:eu-repo/semantics/article
T1 Octapodal Corannulene Porphyrin-Based Assemblies: Allosteric Behavior in Fullerene Hosting
A1 Ferrero, Sergio
A1 Barbero San Juan, Héctor
A1 Miguel, Daniel
A1 García-Rodríguez, Raúl
A1 Álvarez González, Celedonio Manuel
K1 Carbon nanomaterials
K1 Molecular interactions
K1 Nanospheres
K1 Pyrroles
K1 Supramolecular chemistry
K1 2304 Química Macromolecular
AB An octapodal corannulene-based supramolecular system has been prepared by introducing eight corannulene moieties in a porphyrin scaffold. Despite the potential of this double picket fence porphyrin for double-tweezer behavior, NMR titrations show exclusive formation of 1:1 adducts. The system exhibits very strong affinity for C60 and C70 (K1 = (2.71 ± 0.08) × 104 and (2.13 ± 0.1) × 105 M–1, respectively), presenting selectivity for the latter. Density functional theory (DFT) calculations indicate that, in addition to the four corannulene units, the relatively flexible porphyrin tether actively participates in the recognition process, resulting in a strong synergistic effect. This leads to a very strong interaction with C60, which in turn also induces a large structural change on the other face (second potential binding site), leading to a negative allosteric effect. We also introduced Zn2+ in the porphyrin core in an attempt to modulate its flexibility. The resulting metalloporphyrin also displayed single-tweezer behavior, albeit with slightly smaller binding constants for C60 and C70, suggesting that the effect of the coordination of fullerene to one face of our supramolecular platform was still transmitted to the other face, leading to the deactivation of the second potential binding site.
PB American Chemical Society
SN 0022-3263
YR 2020
FD 2020-03-10
LK https://uvadoc.uva.es/handle/10324/65456
UL https://uvadoc.uva.es/handle/10324/65456
LA eng
NO The Journal of Organic Chemistry, marzo 2020, 85, 7, 4918–4926
NO Producción Científica
DS UVaDOC
RD 21-may-2024