11th WCCMS Chile 2018

On the Versatility of Organometallic Calixarenes Towards Anion Recognition

A. O. Ortolan1*, I. Østrøm1, G. F. Caramori1, R. L. T. Parreira2, A. Muñoz-Castro3, F. M. Bickelhaupt4,5.
1
Universidade Federal de Santa Catarina, Brazil. 2 Universidade de Franca, Brazil. 3 Universidad Autonoma de
Chile, Chile. 4 Vrije Universiteit Amsterdam, The Netherlands. 5 Radboud University, The Netherlands.
alexandre.osmar@posgrad.ufsc.br

Non-covalent interactions (NCI) are the main forces involved in the recognition, transport and regulation of many events in
1
biological systems. Although the important role of anionic molecules is well known, the chemistry of anion receptors is still
2 3,4
a growing area. For instance, the anion–π interactions in a series of heterocalixarenes hosts were recently addressed by us.
5
In this connection, Atwood and co-workers reported the synthesis and characterization of a series of macrocyclic complexes
based on calix[4]arene and its derivatives, water soluble and air-stable, possessing an inner hydrophobic cavity suitable to
5,6
incorporate anionic species via noncovalent interactions. Their host capability was confirmed by X-ray crystallography in
− 2− − 6 7
recognizing BF4 , SO4 , and I . Based on these host-guest complexes (Fig. A), we performed a comprehensive electronic-
structure analysis, showing that the anion–π interactions are strengthened and can be efficiently tuned through the proper
choice of the exo-coordinating metal fragment to the host’s arene moieties. Furthermore, the guest’s steric fit in the host
scaffold is a selective and crucial criterion for the anion recognition. The fit of small anions goes with less geometrical
deformation of the host cavity and thus less destabilizing deformation strain upon accommodating the anion. Our quantitative
analyses of the bonding mechanism reveal the most stable host-guest situation occurs in ruthenium complexed hosts, followed
by technetium and molybdenum macrocyclic receptors (Fig. B). The coordinated metals provide a large electrostatic
stabilization to anion recognition, making the calixarene cavity a more electron deficient and turning it into a stronger π-acid.
The interaction is further reinforced by donor–acceptor interactions between the guest’s HOMO and the empty π∗-type orbitals
in the calixarene bowl (Fig. C). Our results highlight the enormous anion-recognition capability of organometallic calixarenes.
We envisage that this will encourage attempts to rationally design and synthesize highly selective hosts.

Acknowledgements: CNPq, CAPES and FAPESP (Brazil). FONDECYT (Chile). NWO (The Netherlands).

References
1. Frontera, A.; Gamez, P.; Mascal, M.; Mooibroek, T. J; Reedijk, J. Angew. Chemie Int. Ed. 2011, 50, 9564-9583.
2. Lehn, J. M. Supramolecular Chemistry. 1995, Wiley-VCH, Weinheim, Germany.
3. Ortolan, A. O.; Caramori, G. F.; Bickelhaupt, F. M.; Parreira, R. L. T.; Muñoz-Castro, A.; Kar, T. Phys. Chem. Chem.
Phys. 2017, 19, 24696−24705.
4. Ortolan, A. O.; Østrøm, I.; Caramori, G. F.; Parreira, R. L. T.; da Silva, E. H.; Bickelhaupt, F. M. J. Phys. Chem. A.
2018, 122, 3328− 3336.
5. Steed, J. W.; Juneja, R. K.; Atwood, J. L. Angew. Chem., Int. Ed. 1995, 33, 2456−2457.
6. Staffilani, M.; Hancock, K. S. B.; Steed, J. W.; Holman, K. T.; Atwood, J. L.; Juneja, R. K.; Burkhalter, R. S. J. Am.
Chem. Soc. 1997, 119, 6324−6335.
7. Ortolan, A. O.; Østrøm, Ina; Caramori, G. F.; Parreira, R. L. T.; Muñoz-Castro, A.; Bickelhaupt, F. M.
Organometallics. 2018, 37, 2167−2176.

A B Cl- C
Mo0 Br -

Tc+ I-
perspective
Ru2+

Host-guest systems metals BF4-

upper view lower view guests guest host-guest host

Concón, Chile, October 15-18, 2018