TY - JOUR
T1 - Self-assembled tetragonal prismatic molecular cage highly selective for anionic π guests
AU - García-Simón, Cristina
AU - Garcia-Borràs, Marc
AU - Gómez, Laura
AU - Garcia-Bosch, Isaac
AU - Osuna, Sílvia
AU - Swart, Marcel
AU - Luis, Josep M.
AU - Rovira, Concepció
AU - Almeida, Manuel
AU - Imaz, Inhar
AU - Maspoch, Daniel
AU - Costas, Miquel
AU - Ribas, Xavi
PY - 2013/1/21
Y1 - 2013/1/21
N2 - The metal-directed supramolecular synthetic approach has paved the way for the development of functional nanosized molecules. In this work, we report the preparation of the new nanocapsule 3×(CF3SO3) 8 with a A4B2 tetragonal prismatic geometry, where A corresponds to the dipalladium hexaazamacrocyclic complex Pd-1, and B corresponds to the tetraanionic form of palladium 5,10,15,20-tetrakis(4- carboxyphenyl)porphyrin (2). The large void space of the inner cavity and the supramolecular affinity for guest molecules towards porphyrin-based hosts converts this nanoscale molecular 3D structure into a good candidate for host-guest chemistry. The interaction between this nanocage and different guest molecules has been studied by means of NMR, UV/Vis, ESI-MS, and DOSY experiments, from which highly selective molecular recognition has been found for anionic, planar-shaped π guests with association constants (K a) higher than 109 M-1, in front of non-interacting aromatic neutral or cationic substrates. DFT theoretical calculations provided insights to further understand this strong interaction. Nanocage 3×(CF3SO3)8 can not only strongly host one single molecule of M(dithiolene)2 complexes (M=Au, Pt, Pd, and Ni), but also can finely tune their optical and redox properties. The very simple synthesis of both the supramolecular cage and the building blocks represents a step forward for the development of polyfunctional supramolecular nanovessels, which offer multiple applications as sensors or nanoreactors. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
AB - The metal-directed supramolecular synthetic approach has paved the way for the development of functional nanosized molecules. In this work, we report the preparation of the new nanocapsule 3×(CF3SO3) 8 with a A4B2 tetragonal prismatic geometry, where A corresponds to the dipalladium hexaazamacrocyclic complex Pd-1, and B corresponds to the tetraanionic form of palladium 5,10,15,20-tetrakis(4- carboxyphenyl)porphyrin (2). The large void space of the inner cavity and the supramolecular affinity for guest molecules towards porphyrin-based hosts converts this nanoscale molecular 3D structure into a good candidate for host-guest chemistry. The interaction between this nanocage and different guest molecules has been studied by means of NMR, UV/Vis, ESI-MS, and DOSY experiments, from which highly selective molecular recognition has been found for anionic, planar-shaped π guests with association constants (K a) higher than 109 M-1, in front of non-interacting aromatic neutral or cationic substrates. DFT theoretical calculations provided insights to further understand this strong interaction. Nanocage 3×(CF3SO3)8 can not only strongly host one single molecule of M(dithiolene)2 complexes (M=Au, Pt, Pd, and Ni), but also can finely tune their optical and redox properties. The very simple synthesis of both the supramolecular cage and the building blocks represents a step forward for the development of polyfunctional supramolecular nanovessels, which offer multiple applications as sensors or nanoreactors. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
KW - cage compounds
KW - density functional calculations
KW - gold anionic guests
KW - host-guest systems
KW - self-assembly
U2 - 10.1002/chem.201203376
DO - 10.1002/chem.201203376
M3 - Article
VL - 19
SP - 1445
EP - 1456
IS - 4
ER -