Document Detail


Self-Assembled Tetragonal Prismatic Molecular Cage Highly Selective for Anionic π Guests.
MedLine Citation:
PMID:  23212936     Owner:  NLM     Status:  Publisher    
Abstract/OtherAbstract:
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⋅(CF(3) SO(3) )(8) with a A(4) B(2) 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 10(9)  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⋅(CF(3) SO(3) )(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.
Authors:
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
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Publication Detail:
Type:  JOURNAL ARTICLE     Date:  2012-12-4
Journal Detail:
Title:  Chemistry (Weinheim an der Bergstrasse, Germany)     Volume:  -     ISSN:  1521-3765     ISO Abbreviation:  Chemistry     Publication Date:  2012 Dec 
Date Detail:
Created Date:  2012-12-5     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  9513783     Medline TA:  Chemistry     Country:  -    
Other Details:
Languages:  ENG     Pagination:  -     Citation Subset:  -    
Copyright Information:
Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Affiliation:
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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