On-Surface Synthesis of Fused Anthracenyl Porphyrin Derivatives

For the last fifteen years, on-surface synthesis became an extremely popular and powerful method to fabricate nanostructures which otherwise would not have been accessible by conventional wet organic syntheses. The syntheses, realized in chamber of high vacuum scanning tunneling microscope (STM), permitted fabrication characterization atomically defined such as polycyclic aromatic hydrocarbons (PAH), graphene nanoribbons or 2D covalent networks. 1 Among molecules studied STM, porphyrins are particular importance because their electronic optical properties. Initial studies were mainly devoted supramolecular organization porphyrin derivatives on surface it is only 2004 that noble metal surfaces used catalytic perform reactions cores. 2 Since then, examples open-shell 3 conjugated oligomers 4 reported. While fused bis- tetra-4,5-bis-(2,4,6-trimethylphenoxy)anthracen-9-yl containing Ni(II) was reported Anderson about 10 years ago, 5 formation π-extended bearing unsubstituted anthracenyl moieties never achieved. compounds possible synthesis. Herein, we report tetra-anthracenylporphyrin via cyclodehydrogenation parent meso-substituted a Au(111) surface. 6 Depending annealing temperature, anthracenylporphyrins with four anthracene fully linked core over-oxidized connected two 2-2’ position observed STM (Figure 1). Figure 1. images tetra-anthracenylporphyrins related structures References Clair, S.; de Oteyza, D. G. Chem. Rev. 2019 , 119 4717-4776. Fox, Boyle, R. W. Commun. 1322-1323. a) Sun, Q.; Mateo, L. M.; Robles, R.; Ruffieux, P.; Lorente, N.; Bottari, G.; Torres, T.; Fasel, J. Am. Soc. 2020 142 18109-18117; b) Zhao, Y.; Jiang, K.; Li, C.; Liu, Xu, Zheng, W.; Guan, D.; H.; Luo, Jia, J.; Zhuang, X.; Wang, S. 18532-18540. S.-X.; Bergkamp, Eimre, Pignedoli, C. A.; Decurtins, T. Angew. Chem., Int. Ed. 59 1334-1339; Sci. 2021 12 247-252. Davis, N. K. Thompson, A. L.; Anderson, H. Org. Lett. 2010 2124-2127; 2011 133 30-31. Baljozović, M. et al. preparation