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Publications 2023


Extended π-Conjugation and Structural Planarity Effects of Symmetrical D-π-A-π-D Naphthalene and Perylene Diimide Semiconductors on n-Type Electrical Properties

S. Gámez-Valenzuela, I. Torres-Moya, A. Sánchez, B. Donoso, J. T. López Navarrete, M. C. Ruiz Delgado, P. Prieto, R. Ponce Ortiz.

Chem. Eur. J. 2023, e202301639. 

A series of donor-π-acceptor-π-donor (D-π-A-π-D) compounds based on naphthalendiimide (NDI) and perylenediimide (PDI) central cores combined with triphenylamine and phenylcarbazole donor groups have been synthesized, characterized and tested in top-contact/bottom gate organic field-effect transistors (OFETs). The results showed high electron mobilities, up to 0.3 cm2 V−1 s−1, in the case of NDI derivatives and moderate values of around 10−3 cm2 V−1 s−1 for PDI-based semiconductors. Quantum chemical calculations were performed in order to support the experimental data. The results suggest that adequate molecular characteristics and larger crystalline domains in NDI vs. PDI semiconducting films may be the reasons behind the enhanced electrical properties of NDI derivatives. Furthermore, when the lateral donor substituents are triphenylamine groups, the mobilities were slightly higher in comparison to phenylcarbazole donor groups due to an improved electron-donating character. Other characterization techniques, such as AFM, X-ray diffraction or spectroelectrochemistry, among others, have been performed to analyze supramolecular order, charge carriers’ nature and stability, parameters closely related to charge transport characteristics.



Understanding the Raman enhancement of carbon nanohorns labelled with organic dyes.

D. Iglesias, R. Martín, M. Á. Álvarez, I. Badía-Domínguez, E. Vázquez, M. C. Ruiz Delgado, P. Prieto, M. A. Herrero.

Nanoscale2023, 15, 12280-12286

Carbon nanohorns have been non-covalently functionalized with two different benzothiadiazoloquinoxalines prepared via Stille cross-coupling reactions under solvent-free conditions and microwave irradiation. The close interactions between these organic molecules and the nanostructures resulted in a prominent Raman enhancement, which makes them attractive candidates for multiple applications. A complete experimental physico-chemical characterization has been combined with in silico studies to understand these phenomena. The processability of the hybrids was exploited to prepare homogeneous films on substrates with different natures.



Easy and Versatile Synthesis of Bulk Quantities of Highly Enriched 13C-Graphene Materials for Biological and Safety Applications.

V. González, J. Frontiñan-Rubio, M. Victoria Gomez, T. Montini, M. Durán-Prado, P. Fornasiero, M. Prato, E. Vázquez.

ACS NANO202317, 1, 606-620

The preparation of bulk quantities of 13C-labeled graphene materials is relevant for basic investigations and for practical applications. In addition, 13C-labeled graphene materials can be very useful in biological and environmental studies, as they may allow the detection of graphene or its derivatives in cells or organs. In this paper, we describe the synthesis of 13C-labeled graphene materials (few-layer graphene, FLG, and graphene oxide, GO) on a tens of mg scale, starting from 13C-labeled methane to afford carbon fibers, followed by liquid-phase exfoliation (FLG) or oxidation (GO). The materials have been characterized by several analytical and microscopic techniques, including Raman and nuclear magnetic resonance spectroscopies, thermogravimetric analysis, X-ray photoelectron spectroscopy, and X-ray powder diffraction. As a proof of concept, the distribution of the title compounds in cells has been investigated. In fact, the analysis of the 13C/12C ratio with isotope ratio mass spectrometry (IRMS) allows the detection and quantification of very small amounts of material in cells or biological compartments with high selectivity, even when the material has been degraded. During the treatment of 13C-labeled FLG with HepG2 cells, 4.1% of the applied dose was found in the mitochondrial fraction, while 4.9% ended up in the nuclear fraction. The rest of the dose did not enter into the cell and remained in the plasma membrane or in the culture media.

doi: 10.1021/acsnano.2c09799

Luminescence colour modulation in benzotriazole-derived waveguides

B. Donoso, I. Torres-Moya, J. Álvarez-Conde, I. Chacón, Á. Díaz-Ortiz, J. Cabanillas-González, P. Prieto.

Dyes and Pigmentes. 2023219, 111583

A series of new Donor-Acceptor-Donor (D-A-D) benzotriazole derivatives have been synthesized and processed into crystals with the aim to establish a relationship between their chemical structure and waveguided luminescent properties. The outcomes show that all crystals display luminescence and active optical waveguiding with optical loss coefficients in the 10−2 dB/μm range, with the capability to tune their luminescence across a wide spectral range of 500–700 nm upon substitution at the benzotriazole moiety. There is also an evident relationship between the HOMO-LUMO energy gaps and the color emission of the corresponding waveguides. These results support the possibility of modulating the emission color of organic waveguides by appropriate chemical functionalization.

DOI: https://doi.org/10.1016/j.dyepig.2023.111583


Multinuclear 1D and 2D NMR with 19F-Photo-CIDNP hyperpolarization in a microfluidic chip with untuned microcoil

Fully automated flow protocol for C(sp3)-C(sp3) bond formation from tertiary amides and alkyl halide

B. Pijper, R. Martín, A. J. Huertas, L. Linares, E. López, J. Llavería, A. de la Hoz, Á. Díaz-Ortiz, D. Dixon, J. Alcázar.

Org. Lett.  2023, ol-2023-013903 

Herein, we present a novel C(sp3)–C(sp3) bond-forming protocol via the reductive coupling of abundant tertiary amides with organozinc reagents prepared in situ from their corresponding alkyl halides. Using a multistep fully automated flow protocol, this reaction could be used for both library synthesis and target molecule synthesis on the gram-scale starting from bench-stable reagents. Additionally, excellent chemoselectivity and functional group tolerance make it ideal for late-stage diversification of druglike molecules.                          


Special Issue: “Organic Chemistry Driven by Academic-Industrial Collaborations”


Donor-acceptor-donor 1H-benzo[d]imidazole derivatives as colored optical waveguides

C. Tardío, J. Álvarez Conde, A. M. Rodríguez, P. Prieto, A. de la Hoz, J. Cabanillas, I. Torres-Moya

Molecules, 2023, 28, 4631

A new series of donor–acceptor–donor (D–A–D) structures derived from arylethynyl 1H-benzo[d]imidazole was synthesized and processed into single crystals with the goal of testing such crystals’ ability to act as optical waveguides. Some crystals displayed luminescence in the 550–600 nm range and optical waveguiding behavior with optical loss coefficients around 10−2 dB/μm, which indicated a notable light transport. The crystalline structure, confirmed by X-ray diffraction, contains internal channels that are important for light propagation, as we previously reported. The combination of a 1D assembly, a single crystal structure, and notable light emission properties with low losses from self-absorption made 1H-benzo[d]imidazole derivatives appealing compounds for optical waveguide applications.

DOI: 10.3390/molecules28124631


Highly Thermally Resistant Bisamide Gelators as Pharmaceutical Crystallization Media

I. Torres-Moya, A. Sánchez, B. Saikia, D. S. Yufit, P. Prieto, J. R. Carrillo, J. W. Steed

Gels 2023, 9, 26

Three simple bisamide derivatives (G1G2 and G3) with different structural modifications were synthesized with easy synthetic procedures in order to test their gel behaviour. The outcomes showed that hydrogen bonding was essential in gel formation; for this reason, only G1 provided satisfactory gels. The presence of methoxy groups in G2 and the alkyl chains in G3 hindered the hydrogen bonding between N-H and C=O that occurred G1. In addition, G1 provided thermally and mechanical stable gels, as confirmed with Tsol and rheology experiments. The gels of G1 were also responsive under pH stimuli and were employed as a vehicle for drug crystallization, causing a change in polymorphism in the presence of flufenamic acid and therefore providing the most thermodynamically stable form III compared with metastable form IV obtained from solution crystallization.