Self-Assembled Tetragonal Prismatic Molecular Cage Highly Selective for Anionic π Guests

Authors

  • Cristina García-Simón,

    1. QBIS Group, Departament de Química, Institut de Química Computacional I Catàlisis (IQCC), Universitat de Girona, Campus Montilivi, E17071 Girona, Catalonia (Spain), Fax: (+34) 972-41-81-50
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  • Marc Garcia-Borràs,

    1. Institut de Química Computacional i Catàlisis (IQCC) and Departament de Química, Universitat de Girona, Campus Montilivi, E17071 Girona, Catalonia (Spain)
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  • Dr. Laura Gómez,

    1. QBIS Group, Departament de Química, Institut de Química Computacional I Catàlisis (IQCC), Universitat de Girona, Campus Montilivi, E17071 Girona, Catalonia (Spain), Fax: (+34) 972-41-81-50
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  • Dr. Isaac Garcia-Bosch,

    1. QBIS Group, Departament de Química, Institut de Química Computacional I Catàlisis (IQCC), Universitat de Girona, Campus Montilivi, E17071 Girona, Catalonia (Spain), Fax: (+34) 972-41-81-50
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  • Dr. Sílvia Osuna,

    1. Institut de Química Computacional i Catàlisis (IQCC) and Departament de Química, Universitat de Girona, Campus Montilivi, E17071 Girona, Catalonia (Spain)
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  • Prof. Marcel Swart,

    1. Institut de Química Computacional i Catàlisis (IQCC) and Departament de Química, Universitat de Girona, Campus Montilivi, E17071 Girona, Catalonia (Spain)
    2. Institució Catalana de Recerca i Estudis Avançats (ICREA), Pg. Lluís Companys 23, E08010 Barcelona, Catalonia (Spain)
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  • Dr. Josep M. Luis,

    1. Institut de Química Computacional i Catàlisis (IQCC) and Departament de Química, Universitat de Girona, Campus Montilivi, E17071 Girona, Catalonia (Spain)
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  • Prof. Concepció Rovira,

    1. Institut de Ciència de Materials de Barcelona (ICMAB-CSIC), Campus UAB, 08193 Bellaterra, Catalonia (Spain)
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  • Prof. Manuel Almeida,

    1. Departamento de Química, IST/ITN, Instituto Superior Técnico / CFMCUL, P-2686-953 Sacavém (Portugal)
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  • Dr. Inhar Imaz,

    1. CIN2(ICN-CSIC), Catalan Institute of Nanotechnology, Esfera UAB, 08193 Bellaterra, Catalonia (Spain)
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  • Prof. Daniel Maspoch,

    1. Institució Catalana de Recerca i Estudis Avançats (ICREA), Pg. Lluís Companys 23, E08010 Barcelona, Catalonia (Spain)
    2. CIN2(ICN-CSIC), Catalan Institute of Nanotechnology, Esfera UAB, 08193 Bellaterra, Catalonia (Spain)
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  • Dr. Miquel Costas,

    Corresponding author
    1. QBIS Group, Departament de Química, Institut de Química Computacional I Catàlisis (IQCC), Universitat de Girona, Campus Montilivi, E17071 Girona, Catalonia (Spain), Fax: (+34) 972-41-81-50
    • QBIS Group, Departament de Química, Institut de Química Computacional I Catàlisis (IQCC), Universitat de Girona, Campus Montilivi, E17071 Girona, Catalonia (Spain), Fax: (+34) 972-41-81-50
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  • Dr. Xavi Ribas

    Corresponding author
    1. QBIS Group, Departament de Química, Institut de Química Computacional I Catàlisis (IQCC), Universitat de Girona, Campus Montilivi, E17071 Girona, Catalonia (Spain), Fax: (+34) 972-41-81-50
    • QBIS Group, Departament de Química, Institut de Química Computacional I Catàlisis (IQCC), Universitat de Girona, Campus Montilivi, E17071 Girona, Catalonia (Spain), Fax: (+34) 972-41-81-50
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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 (Ka) higher than 109M−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.

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