Supramolecular Mask-Mediated Regioselective bis-Bingel-Functionalization of M3N@Ih-C80 (M = Lu, Sc).
7 affiliations
- 1Institut de Química Computacional i Catàlisi (IQCC) and Departament de Química, Universitat de Girona, Campus Montilivi, 17003Girona, Catalonia, Spain.
- 2Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, Piscataway, New Jersey08854, United States.
- 3Instituto de Nanociencia y Materiales de Aragon (INMA), CSIC-Universidad de Zaragoza, C/ Pedro Cerbuna 12, 50009Zaragoza, Spain.
- 4Servei de RMN, Facultat de Ciències, Universitat Autònoma de Barcelona, Campus UAB, 08193Bellaterra, Catalonia, Spain.
- 5Materials Science Institute of Madrid - CSIC, 28049Madrid, Spain.
- 6Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC and The Barcelona Institute of Science and Technology, Campus UAB, 08193Bellaterra, Catalonia, Spain.
- 7ICREA, Pg. Lluís Companys 23, 08010Barcelona, Catalonia, Spain.
Abstract
Exohedral functionalization of endohedral metallofullerenes (EMFs) is essential for exploiting these intriguing molecules as novel materials in applications such as biomedicine and organic solar cell device design. In the case of trimetallic nitride template EMFs (TNT-EMFs), many functionalization methods effective for empty fullerenes are inaccessible or less efficient due to the presence of the encapsulated cluster. This inner cluster increases the electron density on the carbon cage surface, reducing its reactivity. Moreover, it has been demonstrated that the inner cluster controls both the reactivity and regioselectivity of bare TNT-EMFs. The supramolecular mask strategy (SMS) has yielded promising results in the functionalization of C60 and C70 and, for the first time, is applied here to endohedral fullerenes to achieve mono- and bis-functionalization of Lu3N@Ih-C80 and Sc3N@Ih-C80. Encapsulation of both TNT-EMFs within a tetragonal prismatic cage host is crucial for enhancing their reactivity, enabling bis-functionalization under milder conditions and with shorter reaction times. Comprehensive spectroscopic and spectrometric characterization, combined with molecular dynamics (MD) simulations and density functional theory (DFT) calculations, identified the most favorable and stable bis-adducts by considering the positive alignment between the geometry imposed by the inner cluster and that allowed by the tetragonal prismatic nanocapsule mask. This resulted in preferential formation of five bis-adducts (out of 27 possible), two of them bearing a 120° angle between the addends and aligning with the inner TNT cluster trigonal geometry.
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BibTeX
@article{iannace2026supramolecular,
title = {{Supramolecular Mask-Mediated Regioselective bis-Bingel-Functionalization of M3N@Ih-C80 (M = Lu, Sc).}},
author = {Valentina Iannace and Clara Sabrià and Sheng Zhu and Olga A Stasyuk and Miquel Solà and Teodor Parella and Sergio Fernández and Felipe Gándara and Inhar Imaz and Daniel Maspoch and Jianyuan Zhang and Ferran Feixas and Xavi Ribas},
journal = {Journal of the American Chemical Society},
year = {2026},
month = oct,
doi = {10.1021/jacs.6c16243},
url = {https://europepmc.org/article/MED/42954585},
note = {CC BY},
}
RIS
TY - JOUR
TI - Supramolecular Mask-Mediated Regioselective bis-Bingel-Functionalization of M3N@Ih-C80 (M = Lu, Sc).
AU - Valentina Iannace
AU - Clara Sabrià
AU - Sheng Zhu
AU - Olga A Stasyuk
AU - Miquel Solà
AU - Teodor Parella
AU - Sergio Fernández
AU - Felipe Gándara
AU - Inhar Imaz
AU - Daniel Maspoch
AU - Jianyuan Zhang
AU - Ferran Feixas
AU - Xavi Ribas
PY - 2026
DA - 2026/10/01
JO - Journal of the American Chemical Society
DO - 10.1021/jacs.6c16243
UR - https://europepmc.org/article/MED/42954585
AB - Exohedral functionalization of endohedral metallofullerenes (EMFs) is essential for exploiting these intriguing molecules as novel materials in applications such as biomedicine and organic solar cell device design. In the case of trimetallic nitride template EMFs (TNT-EMFs), many functionalization methods effective for empty fullerenes are inaccessible or less efficient due to the presence of the encapsulated cluster. This inner cluster increases the electron density on the carbon cage surface, reducing its reactivity. Moreover, it has been demonstrated that the inner cluster controls both the reactivity and regioselectivity of bare TNT-EMFs. The supramolecular mask strategy (SMS) has yielded promising results in the functionalization of C60 and C70 and, for the first time, is applied here to endohedral fullerenes to achieve mono- and bis-functionalization of Lu3N@Ih-C80 and Sc3N@Ih-C80. Encapsulation of both TNT-EMFs within a tetragonal prismatic cage host is crucial for enhancing their reactivity, enabling bis-functionalization under milder conditions and with shorter reaction times. Comprehensive spectroscopic and spectrometric characterization, combined with molecular dynamics (MD) simulations and density functional theory (DFT) calculations, identified the most favorable and stable bis-adducts by considering the positive alignment between the geometry imposed by the inner cluster and that allowed by the tetragonal prismatic nanocapsule mask. This resulted in preferential formation of five bis-adducts (out of 27 possible), two of them bearing a 120° angle between the addends and aligning with the inner TNT cluster trigonal geometry.
SN - 0002-7863
SN - 1520-5126
ER -