Interplay between π-Conjugation and Exchange Magnetism in One-Dimensional Porphyrinoid Polymers

• DOI: 10.1021/jacs.2c02700
• Publication Date: 2022-07-11T23:41:25Z
• Authors: Kalyan Biswas; Maxence Urbani; Ana Sánchez-Grande; Diego Soler-Polo; Koen Lauwaet; Adam Matěj; Pingo Mutombo; Libor Veis; Jiri Brabec; Katarzyna Pernal; José M. Gallego; Rodolfo Miranda; David Écija; Pavel Jelínek; Tomás Torres; José I. Urgel
• Keywords: Magnetism; Open shell

The synthesis of novel polymeric materials with porphyrinoid compounds as key components the repeating units attracts widespread interest from several scientific fields in view their extraordinary variety functional properties potential applications a wide range highly significant technologies. vast majority such polymers present closed-shell ground state, and, only recently, result improved synthetic strategies, engineering open-shell spin delocalization along conjugation length has been achieved. Here, we combined strategy toward fabrication one-dimensional porphyrinoid-based homocoupled via surface-catalyzed [3 + 3] cycloaromatization isopropyl substituents on Au(111). Scanning tunneling microscopy and noncontact atomic force describe thermal-activated intra- intermolecular oxidative ring closure reactions well controlled tip-induced hydrogen dissociation units. In addition, scanning spectroscopy measurements, complemented by computational investigations, reveal character, that is, antiferromagnetic singlet state (S = 0) formed polymers, characterized singlet-triplet inelastic excitations observed between spins adjacent Our approach sheds light crucial relevance π-conjugation correlations spins, while expanding on-surface toolbox opening avenues innovative nanomaterials prospects carbon-based spintronics.