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The authors acknowledge to several funding organizations for their financial support. We thank support from the '(MAD2D-CM)-IMDEA-Nanociencia' project funded by Comunidad de Madrid, by the Recovery, Transformation and Resilience Plan, and by NextGenerationEU from the European Union, and from the Spanish Ministry of Science, Innovation and Universities (Project PID2022-136961NB-I00 and PID2023-152793NA-I00). IMDEA Nanociencia also acknowledges the "Severo Ochoa" Programme for Centers of Excellence in R&D (MINECO, Grant SEV-2016-0686 and CEX2020-001039-S). We appreciate funding from the Praemium Academie of the Academy of Science of the Czech Republic and the CzechNanoLab Research Infrastructure supported by MEYS CR (LM2018110). P.J. thanks the support of the GACR 23-05486S. This work was supported by European Structural and Investment Funds and the Czech Ministry of Education, Youth and Sports (Project No TERAFIT - CZ.02.01.01/00/22_008/0004594). X.F. acknowledge the EU Graphene Flagship (Graphene Core 3, 881603) and EIC-2022-Pathfinder Open (ATYPIQUAL, 101099098). J.M. acknowledge the financial support from the National Natural Science Foundation of China (No. 92463307). J.I.U. acknowledge the funding from MCIU for the Ramon y Cajal (RYC2022-037352). A.B. and A.G. thank the Juan de la Cierva (FJC2021-046524-I, JDC2022-048249-I) program, respectively. A.G. also acknowledges the H2020-MSCA-COFUND-2020 program. Open Access publishing facilitated by Fyzikalni ustav Akademie ved Ceske republiky, as part of the Wiley - CzechELib agreement.

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Reactivity and Magnetic Coupling of Triangulene Dimers Linked via para-Biphenyl Units

Publicado en:ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (): - - 2025-02-28 64(17), DOI: 10.1002/anie.202501874

Autores: Pérez-Elvira E; Lozano M; Huang Q; Ma J; Gallardo A; Barragán A; Lauwaet K; Gallego JM; Miranda R; Jelínek P; Écija D; Soler-Polo D; Feng X; Urgel JI

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Triangulene and its homologues are promising building blocks for high-spin low-dimensional networks with long-range magnetic order. Despite the recent progress in the synthesis and characterization of coupled triangulenes, key parameters such as the number of organic linking units or their dihedral angles remain scarce, making further studies crucial for an essential understanding of their implications. Here, we investigate the synthesis and reactivity of two triangulene dimers linked by two (Dimer 1) or one (Dimer 2) para-biphenyl units, respectively, on a metal surface in an ultra-high vacuum environment. First-principles calculations and model Hamiltonians reveal how spin excitation and radical character depend on the rotation of the para-biphenyl units. Comprehensive scanning tunneling microscopy (STM) in combination with density functional theory (DFT) calculations confirm the successful formation of Dimer 1 on Au(111). Non-contact atomic force microscopy (nc-AFM) measurements resolve the twisted conformation of the linking para-biphenyl units for Dimer 1. On the contrary, the inherent flexibility of Dimer 2 induces the planarization of the para-biphenyl, resulting in the spontaneous formation of two additional five-membered rings per dimer connected by a single C-C bond (Dimers 2 '). Furthermore, scanning tunneling spectroscopy (STS) measurements confirm the antiferromagnetic (S=0) coupling of the observed dimers, underscoring the critical influence of dihedral angles and structural flexibility of the linking units in pi-electron magnetic nanostructures.

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