Staff directory Leyre Gómez Navascués

Publications

2021

  • A three-shell supramolecular complex enables the symmetry-mismatched chemo- and regioselective bis-functionalization of C60

    Ubasart E., Borodin O., Fuertes-Espinosa C., Xu Y., García-Simón C., Gómez L., Juanhuix J., Gándara F., Imaz I., Maspoch D., von Delius M., Ribas X. Nature Chemistry; 2021. 10.1038/s41557-021-00658-6. IF: 21.687

    Molecular Russian dolls (matryoshkas) have proven useful for testing the limits of preparative supramolecular chemistry but applications of these architectures to problems in other fields are elusive. Here we report a three-shell, matryoshka-like complex—in which C60 sits inside a cycloparaphenylene nanohoop, which in turn is encapsulated inside a self-assembled nanocapsule—that can be used to address a long-standing challenge in fullerene chemistry, namely the selective formation of a particular fullerene bis-adduct. Spectroscopic evidence indicates that the ternary complex is sufficiently stable in solution for the two outer shells to affect the addition chemistry of the fullerene guest. When the complex is subjected to Bingel cyclopropanation conditions, the exclusive formation of a single trans-3 fullerene bis-adduct was observed in a reaction that typically yields more than a dozen products. The selectivity facilitated by this matryoshka-like approach appears to be a general phenomenon and could be useful for applications where regioisomerically pure C60 bis-adducts have been shown to have superior properties compared with isomer mixtures. [Figure not available: see fulltext.] © 2021, The Author(s), under exclusive licence to Springer Nature Limited.


  • Room temperature synthesis and characterization of novel lead-free double perovskite nanocrystals with a stable and broadband emission

    Tang Y., Gomez L., Van Der Laan M., Timmerman D., Sebastian V., Huang C.-C., Gregorkiewicz T., Schall P. Journal of Materials Chemistry C; 9 (1): 158 - 163. 2021. 10.1039/d0tc04394j. IF: 7.059

    Low-dimensional and lead-free halide perovskites are of great interest for their wide application potential for optoelectronic applications. We report on the successful synthesis of novel lead-free colloidal Cs3BiBr6 nanocrystals (NCs) with an ultra-small size of ∼1.5-3 nm by a room temperature antisolvent process. From crystallographic characterization we show that it is critical to precisely control the ratio of precursors to obtain the pure 3-1-6 phase. The synthesis process is facile and repeatable and results in Cs3BiBr6 NCs that display stable blue emission around 438 nm with a relatively broad linewidth of 92.1 nm. Low-temperature photoluminescence (PL) measurements displayed a red-shift of bandgap with decreasing temperature, which might be attributed to the thermal expansion of the lattice. In addition, the NCs demonstrate high stability at ambient conditions. This journal is © The Royal Society of Chemistry.


2020

  • Highly Stable Perovskite Supercrystals via Oil-in-Oil Templating

    Tang Y., Gomez L., Lesage A., Marino E., Kodger T.E., Meijer J.-M., Kolpakov P., Meng J., Zheng K., Gregorkiewicz T., Schall P. Nano Letters; 20 (8): 5997 - 6004. 2020. 10.1021/acs.nanolett.0c02005. IF: 11.238

    Inorganic perovskites display an enticing foreground for their wide range of optoelectronic applications. Recently, supercrystals (SCs) of inorganic perovskite nanocrystals (NCs) have been reported to possess highly ordered structure as well as novel collective optical properties, opening new opportunities for efficient films. Here, we report the large-scale assembly control of spherical, cubic, and hexagonal SCs of inorganic perovskite NCs through templating by oil-in-oil emulsions. We show that an interplay between the roundness of the cubic NCs and the tension of the confining droplet surface sets the superstructure morphology, and we exploit this interplay to design dense hyperlattices of SCs. The SC films show strongly enhanced stability for at least two months without obvious structural degradation and minor optical changes. Our results on the controlled large-scale assembly of perovskite NC superstructures provide new prospects for the bottom-up production of optoelectronic devices based on the microfluidic production of mesoscopic building blocks. © 2020 American Chemical Society.


  • Supramolecular Fullerene Sponges as Catalytic Masks for Regioselective Functionalization of C60

    Fuertes-Espinosa C., García-Simón C., Pujals M., Garcia-Borràs M., Gómez L., Parella T., Juanhuix J., Imaz I., Maspoch D., Costas M., Ribas X. Chem; 6 (1): 169 - 186. 2020. 10.1016/j.chempr.2019.10.010. IF: 19.375

    Isomer-pure poly-functionalized fullerenes are required to boost the development of fullerene chemistry in all fields. On a general basis, multi-adduct mixtures with uncontrolled regioselectivity are obtained, and the use of chromatographic purification is prohibitively costly and time consuming, especially in the production of solar cells. Single-isomer poly-functionalized fullerenes are only accessible via stoichiometric, multistep paths entailing protecting-unprotecting sequences. Herein, a nanocapsule is used as a supramolecular tetragonal prismatic mask to exert full control on the reactivity and the equatorial regioselectivity of Bingel-Hirsch cyclopropanation reactions of a confined C60 guest. Thus, equatorial bis-, tris-, and tetrakis-C60 homo-adducts are exclusively obtained in a stepwise manner. Furthermore, isomer-pure equatorial hetero-tetrakis-adducts or hetero-Th-hexakis-adducts are synthesized at will in one-pot synthesis for the first time. 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 biomedical applications. Video Abstract: The supramolecular mask protocol is a significant step forward for the regioselective functionalization of fullerenes. The exquisite ability to form pure-isomer poly-functionalized C60 adducts, overcoming tedious and non-practical chromatographic separations, allows for their direct testing in solar cell prototypes. Furthermore, the supramolecular mask strategy can be applied to C70 or higher fullerenes, opening a plethora of poly-functionalized fullerene derivatives to be synthesized and tested. Moreover, apart from the nucleophilic cyclopropanations reported herein, the protocol is currently being expanded to Diels-Alder (DA), 1,3-dipolar cycloadditions and PC60BM-type cyclopropanations, thus enabling a variety of regioselective functionalization reactions. This supramolecular mask strategy can help the discovery of the next generation of improved solar cells (organic or perovskite based) or new drug candidates. An unprecedented and straightforward supramolecular mask strategy to prepare exclusively equatorial bis-, tris-, and tetrakis-cyclopropanated-C60 Bingel-Hirsch derivatives is reported. By taking advantage of the high affinity for fullerene of tetragonal prismatic supramolecular cages, a highly stable C60⊂1a·(BArF)8 host-guest complex is submitted to Bingel-Hirsch cyclopropanation reaction conditions. Regioselectivity is strictly dictated by the four cross-shaped apertures of the nanocapsule in a controlled fashion. Moreover, stepwise-cyclopropanated adducts up to tetrakis additions are obtained in excellent yields and purities. © 2019 Elsevier Inc.