Self-Assembled Tetragonal Prismatic Molecular Cage Highly Selective for Anionic π Guests
dc.contributor.author
dc.date.accessioned
2013-12-02T14:05:10Z
dc.date.available
2013-12-02T14:05:10Z
dc.date.issued
2013
dc.identifier.issn
0947-6539
dc.identifier.uri
dc.description.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 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
dc.description.sponsorship
We are grateful for financial support from the MICINN of Spain (CTQ2009-08464/BQU to M. C., CTQ2011-25086/BQU, CTQ2011-23156/BQU, PhD grant AP2010-2517 to M. G. B, INNPLANTA- INP-2011-0059PCT-420000-ACT1 and Consolider-Ingenio CSD2010-00065), the FEDER fund (European Fund for Regional Development) for the grant UNGI08-4E-003, the European Research Council for Project ERC-2011StG-277801 to X. R. and ERC-2008-StG-29910 to M. C., and the Generalitat de Catalunya (2009SGR637, 2009SGR528, and a Ph.D. grant to C. G. S.). X. R. and M. C. thank ICREA-Academia awards. I. I. thanks MINECO for a Ramon y Cajal contract. We thank Dr. Teodor Parella for fruitful discussions. We thank STR's from UdG for technical support, and we also acknowledge the computer resources, technical expertise, and assistance provided by the Barcelona Supercomputing Center Centro Nacional de Supercomputacion, and Centre de Serveis Cientifics i Academics de Catalunya (CESCA) for partial funding of computer time
dc.format.mimetype
application/pdf
dc.language.iso
eng
dc.publisher
Wiley-VCH Verlag Berlin
dc.relation
MICINN/PN 2010-2012/CTQ2009-08464
info:eu-repo/grantAgreement/MICINN//CTQ2011-23156/ES/AVANCES EN CATALISIS Y AROMATICIDAD/
info:eu-repo/grantAgreement/MICINN//CTQ2011-25086/ES/MODELIZACION MULTIESCALAR EN (BIO)QUIMICA/
MICINN/PN 2010-2016/CSD2010-00065
AGAUR/2009-2014/2009 SGR-637
AGAUR/2009-2014/2009 SGR-528
MICINN/PN 2011/INP-2011-0059-PCT-420000
dc.relation.isformatof
Reproducció digital del document publicat a: http://dx.doi.org/10.1002/chem.201203376
dc.relation.ispartof
© Chemistry : a European Journal, 2013, vol. 19, p. 1445-1456
dc.relation.ispartofseries
Articles publicats (D-Q)
dc.rights
Tots els drets reservats
dc.title
Self-Assembled Tetragonal Prismatic Molecular Cage Highly Selective for Anionic π Guests
dc.type
info:eu-repo/semantics/article
dc.rights.accessRights
info:eu-repo/semantics/embargoedAccess
dc.embargo.terms
Cap
dc.date.embargoEndDate
info:eu-repo/date/embargoEnd/2026-01-01
dc.relation.projectID
info:eu-repo/grantAgreement/EC/FP7/277801/EU/Sustainable C-X and C-H Functionalization Catalyzed by Copper(III) Species/SUSCATCU3
info:eu-repo/grantAgreement/EC/FP7/239910/EU/Bio-inspired Design of Catalysts for Selective Oxidations of C-H and C=C Bonds/BIDECASEOX
dc.type.version
info:eu-repo/semantics/publishedVersion
dc.identifier.doi
dc.contributor.funder
dc.relation.ProjectAcronym
dc.identifier.eissn
1521-3765