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Self‐Assembled Tetragonal Prismatic Molecular Cage Highly Selective for Anionic π Guests
Author(s) -
GarcíaSimón Cristina,
GarciaBorràs Marc,
Gómez Laura,
GarciaBosch Isaac,
Osuna Sílvia,
Swart Marcel,
Luis Josep M.,
Rovira Concepció,
Almeida Manuel,
Imaz Inhar,
Maspoch Daniel,
Costas Miquel,
Ribas Xavi
Publication year - 2013
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201203376
Subject(s) - supramolecular chemistry , nanocages , molecule , porphyrin , cationic polymerization , tetragonal crystal system , chemistry , nanoreactor , crystallography , molecular recognition , nanotechnology , materials science , photochemistry , crystal structure , polymer chemistry , organic chemistry , catalysis
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.