Self-assembled tetragonal prismatic molecular cage highly selective for anionic π guests

Cristina García-Simón, Marc Garcia-Borràs, Laura Gómez, Isaac Garcia-Bosch, Sílvia Osuna, Marcel Swart, Josep M. Luis, Concepció Rovira, Manuel Almeida, Inhar Imaz, Daniel Maspoch, Miquel Costas, Xavi Ribas

    Research output: Contribution to journalArticleResearchpeer-review

    25 Citations (Scopus)

    Abstract

    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.
    Original languageEnglish
    Pages (from-to)1445-1456
    JournalChemistry - A European Journal
    Volume19
    Issue number4
    DOIs
    Publication statusPublished - 21 Jan 2013

    Keywords

    • cage compounds
    • density functional calculations
    • gold anionic guests
    • host-guest systems
    • self-assembly

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