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Supramolecular Fullerene Sponges As Catalytic Masks for Regioselective Functionalization of C 60

94 Pages Posted: 4 Aug 2019 Sneak Peek Status: Review Complete

See all articles by Carles Fuertes-Espinosa

Carles Fuertes-Espinosa

University of Girona - Institute of Computational Chemistry and Catalysis-Institut de Química Computacional i Catàlisi

Cristina García-Simón

University of Girona - Institute of Computational Chemistry and Catalysis-Institut de Química Computacional i Catàlisi

Míriam Pujals

University of Girona - Institute of Computational Chemistry and Catalysis-Institut de Química Computacional i Catàlisi

Marc Garcia-Borràs

University of Girona - Institute of Computational Chemistry and Catalysis-Institut de Química Computacional i Catàlisi

Laura Gómez

University of Girona

Teodor Parella

Autonomous University of Barcelona

Judit Juanhuix

ALBA Synchrotron

Inhar Imaz

Barcelona Institute of Science and Technology (BIST)

Daniel Maspoch

Barcelona Institute of Science and Technology (BIST)

Miquel Costas

University of Girona - Institute of Computational Chemistry and Catalysis-Institut de Química Computacional i Catàlisi

Xavi Ribas

University of Girona - Institute of Computational Chemistry and Catalysis-Institut de Química Computacional i Catàlisi; University of Girona - Department of Chemistry- Departament de Química

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Abstract

Isomer-pure poly-functionalizalized fullerenes are required to boost the development of fullerene chemistry in any field, and specifically in solar cell design. Easy-accessible mono-functionalized fullerenes are mainly used in organic- or perovskite-based solar cells, due to the hampered accessibility to pure-isomer poly-adduct derivatives. In a general basis, multi-adduct mixtures with uncontrolled regioselectivity are obtained, and chromatographic purification is prohibitively costly and time-consuming to be used in the production of solar cells. Moreover, single isomer poly-functionalized fullerenes are only accessible via stoichiometric, multistep paths entailing protecting-unprotecting sequences. Herein, a nanocapsule is used as a supramolecular mask to exert full control on the reactivity and the equatorial regioselectivity of Bingel-Hirsch cyclopropanation reactions of confined fullerene guests. Thus, equatorial bis-, tris- and tetrakis-C60 homo-adducts are exclusively obtained in a stepwise manner, completely avoiding over functionalization (always observed in bulk solution) and holding precise control on the number of additions. Regioselectivity is strictly dictated by the four cross-shaped open windows in the tetragonal prismatic supramolecular container. Furthermore, isomer-pure equatorial hetero-tetrakis-adducts or hetero-Th-hexakis-adducts are synthesized at will in one-pot synthesis for the first time. Remarkably, a synthetically useful biphasic protocol is designed to achieve selective and quantitative formation of exclusively tetrakis-adducts using catalytic amounts of nanocapsule. Therefore, the confinement control imposed by the capsule’s cavity conforms a unique practical strategy to infer regio-control to the synthesis of fullerene equatorial poly-adducts. This work provides a synthetically valuable path to produce a plethora of new pure-isomer poly-functionalized C60-based compounds, as candidates for testing in solar cell devices and for biomedical applications.

Keywords: Regioselective functionalization of C60, supramolecular mask strategy, homo-adduct and hetero-adduct fullerene derivatives, electron transport layer for solar cells, synthetically useful catalytic approach, host-guest chemistry, chemistry at confined space

Suggested Citation

Fuertes-Espinosa, Carles and García-Simón, Cristina and Pujals, Míriam and Garcia-Borràs, Marc and Gómez, Laura and Parella, Teodor and Juanhuix, Judit and Imaz, Inhar and Maspoch, Daniel and Costas, Miquel and Ribas, Xavi, Supramolecular Fullerene Sponges As Catalytic Masks for Regioselective Functionalization of C 60 (August 1, 2019). CHEMJOURNAL-D-19-00766. Available at SSRN: https://ssrn.com/abstract=3430708 or http://dx.doi.org/10.2139/ssrn.3430708
This is a paper under consideration at Cell Press and has not been peer-reviewed.

Carles Fuertes-Espinosa

University of Girona - Institute of Computational Chemistry and Catalysis-Institut de Química Computacional i Catàlisi ( email )

Campus Montilivi
Catalonia, E-17003
Spain

Cristina García-Simón

University of Girona - Institute of Computational Chemistry and Catalysis-Institut de Química Computacional i Catàlisi ( email )

Campus Montilivi
Catalonia, E-17003
Spain

Míriam Pujals

University of Girona - Institute of Computational Chemistry and Catalysis-Institut de Química Computacional i Catàlisi ( email )

Campus Montilivi
Catalonia, E-17003
Spain

Marc Garcia-Borràs

University of Girona - Institute of Computational Chemistry and Catalysis-Institut de Química Computacional i Catàlisi ( email )

Campus Montilivi
Catalonia, E-17003
Spain

Laura Gómez

University of Girona ( email )

Girona, 17071
Spain

Teodor Parella

Autonomous University of Barcelona ( email )

Plaça Cívica
Cerdañola del Valles
Barcelona, Barcelona 08193
Spain

Judit Juanhuix

ALBA Synchrotron ( email )

Catalonia, E-08290
Spain

Inhar Imaz

Barcelona Institute of Science and Technology (BIST) ( email )

Carrer del Comte d’Urgell 187
Building 12 (BIST)
Barcelona, 08036
Spain

Daniel Maspoch

Barcelona Institute of Science and Technology (BIST) ( email )

Carrer del Comte d’Urgell 187
Building 12 (BIST)
Barcelona, 08036
Spain

Miquel Costas

University of Girona - Institute of Computational Chemistry and Catalysis-Institut de Química Computacional i Catàlisi ( email )

Campus Montilivi
Catalonia, E-17003
Spain

Xavi Ribas (Contact Author)

University of Girona - Institute of Computational Chemistry and Catalysis-Institut de Química Computacional i Catàlisi ( email )

Campus Montilivi
Catalonia, E-17003
Spain

University of Girona - Department of Chemistry- Departament de Química ( email )

Catalonia, E-17003
Spain

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