Tuning Heterocalixarenes to Improve Their Anion Recognition: A Computational Approach

Alexandre O. Ortolan; Ina Østrøm; Giovanni F. Caramori; Renato L.T. Parreira; Eder H. Da Silva; F. Matthias Bickelhaupt

doi:10.1021/acs.jpca.8b01866

Tuning Heterocalixarenes to Improve Their Anion Recognition: A Computational Approach

Alexandre O. Ortolan
, Ina Østrøm
, Giovanni F. Caramori^*
, Renato L.T. Parreira
, Eder H. Da Silva
, F. Matthias Bickelhaupt

^*Corresponding author for this work

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Research output: Contribution to Journal › Article › Academic › peer-review

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Abstract

We have explored and analyzed the physical factors through which noncovalent interactions in anion sensing based on calixarene-type hosts can be tuned, using dispersion-corrected DFT and Kohn-Sham molecular orbital (KS-MO) theory in conjunction with a canonical energy decomposition analysis (EDA). We find that the host-guest interaction can be enhanced through the introduction of strongly electron-withdrawing groups at particular positions of the arene and triazine units in the host molecule as well as by coordination of a metal complex to the arene and triazine rings. Our analyses reveal that the enhanced anion affinity is caused by increasing the electrostatic potential in the heterocalixarene cavities. This insight can be employed to further tune and improve their selectivity for chloride ions.

Original language	English
Pages (from-to)	3328-3336
Number of pages	9
Journal	Journal of Physical Chemistry A
Volume	122
Issue number	12
Early online date	15 Mar 2018
DOIs	https://doi.org/10.1021/acs.jpca.8b01866
Publication status	Published - 29 Mar 2018

Funding

A.O.O. thanks CNPq for his PhD scholarship (Grant 142339/ 2015-6). G.F.C. thanks CNPq (Grant 302408/2014-2) for the research fellowship. I.Ø. thanks CAPES for a Master’s scholarship (Grant 1732086). R.L.T.P. thanks FAPESP (Grant 2011/07623-8) and CAPES (Science without Borders program, Grant 88881.068346/2014-01) for financial support. F.M.B. thanks The Netherlands Organisation for Scientific Research (NWO) for financial support. A.O.O. thanks CNPq for his PhD scholarship (Grant 142339/2015-6). G.F.C. thanks CNPq (Grant 302408/2014-2) for the research fellowship. I. thanks CAPES for a Master's scholarship (Grant 1732086). R.L.T.P. thanks FAPESP (Grant 2011/07623-8) and CAPES (Science without Borders program, Grant 88881.068346/2014-01) for financial support.

Funders	Funder number
Nederlandse Organisatie voor Wetenschappelijk Onderzoek
Science without Borders program
Coordenação de Aperfeiçoamento de Pessoal de Nível Superior	88881.068346/2014-01, 1732086
Fundação de Amparo à Pesquisa do Estado de São Paulo	2011/07623-8, 88881.068346/2014-01
Conselho Nacional de Desenvolvimento Científico e Tecnológico	302408/2014-2, 142339/ 2015-6

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This output contributes to the following UN Sustainable Development Goals (SDGs)

SDG 7 Affordable and Clean Energy

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10.1021/acs.jpca.8b01866

Tuning Heterocalixarenes to Improve Their Anion Recognition A Computational ApproachFinal published version, 3.27 MBLicence: Article 25fa Dutch Copyright Act

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abstract = "We have explored and analyzed the physical factors through which noncovalent interactions in anion sensing based on calixarene-type hosts can be tuned, using dispersion-corrected DFT and Kohn-Sham molecular orbital (KS-MO) theory in conjunction with a canonical energy decomposition analysis (EDA). We find that the host-guest interaction can be enhanced through the introduction of strongly electron-withdrawing groups at particular positions of the arene and triazine units in the host molecule as well as by coordination of a metal complex to the arene and triazine rings. Our analyses reveal that the enhanced anion affinity is caused by increasing the electrostatic potential in the heterocalixarene cavities. This insight can be employed to further tune and improve their selectivity for chloride ions.",

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AU - Parreira, Renato L.T.

AU - Da Silva, Eder H.

AU - Bickelhaupt, F. Matthias

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AB - We have explored and analyzed the physical factors through which noncovalent interactions in anion sensing based on calixarene-type hosts can be tuned, using dispersion-corrected DFT and Kohn-Sham molecular orbital (KS-MO) theory in conjunction with a canonical energy decomposition analysis (EDA). We find that the host-guest interaction can be enhanced through the introduction of strongly electron-withdrawing groups at particular positions of the arene and triazine units in the host molecule as well as by coordination of a metal complex to the arene and triazine rings. Our analyses reveal that the enhanced anion affinity is caused by increasing the electrostatic potential in the heterocalixarene cavities. This insight can be employed to further tune and improve their selectivity for chloride ions.

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Tuning Heterocalixarenes to Improve Their Anion Recognition: A Computational Approach

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