Steering Large Magnetic Exchange Coupling in Nanographenes near the Closed-Shell to Open-Shell Transition

• DOI: 10.1021/jacs.2c11431
• Publication Date: 2023-01-28T13:56:50Z
• Authors: Kalyan Biswas; Diego Soler; Shantanu Mishra; Qiang Chen; Xuelin Yao; Ana Sánchez-Grande; Kristjan Eimre; Pingo Mutombo; Cristina Martín-F...; Koen Lauwaet; José M. Gallego; Pascal Ruffieux; Carlo A. Pignedoli; Klaus Müllen; Rodolfo Miranda; José I. Urgel; Akimitsu Narita; Roman Fasel; Pavel Jelínek; David Écija
• Keywords: 02 engineering and technology; Molecules; Quantum mechanics; 01 natural sciences; 7. Clean energy; Nanostructures; 0104 chemical sciences; Magnetic properties; Scanning tunneling microscopy; 0210 nano-technology

The design of open-shell carbon-based nanomaterials is at the vanguard of materials science, steered by their beneficial magnetic properties like weaker spin-orbit coupling than that of transition metal atoms and larger spin delocalization, which are of potential relevance for future spintronics and quantum technologies. A key parameter in magnetic materials is the magnetic exchange coupling (MEC) between unpaired spins, which should be large enough to allow device operation at practical temperatures. In this work, we theoretically and experimentally explore three distinct families of nanographenes (NGs) (A, B, and C) featuring majority zigzag peripheries. Through many-body calculations, we identify a transition from a closed-shell ground state to an open-shell ground state upon an increase of the molecular size. Our predictions indicate that the largest MEC for open-shell NGs occurs in proximity to the transition between closed-shell and open-shell states. Such predictions are corroborated by the on-surface syntheses and structural, electronic, and magnetic characterizations of three NGs (A[3,5], B[4,5], and C[4,3]), which are the smallest open-shell systems in their respective chemical families and are thus located the closest to the transition boundary. Notably, two of the NGs (B[4,5] and C[4,3]) feature record values of MEC (close to 200 meV) measured on the Au(111) surface. Our strategy for maximizing the MEC provides perspectives for designing carbon nanomaterials with robust magnetic ground states.