Polymerization of Porphyrins by Indenyl Coupling

Abstract Porphyrin polymers merge the photophysical, electrochemical, sensory and catalytic properties of porphyrins with the processability and robustness of polymeric materials, offering versatile and synergetic platforms for optoelectronics and catalysis. Here we report an on-surface strategy for the atomically precise polymerization of porphyrins via regioselective indenyl coupling. Deposition of an indenyl-functionalized porphyrin on Au(111) and sequential annealing drives a stepwise transformation: cyclodehydrogenation at 100 °C planarizes the precursor into π-extended porphyrins, while annealing above 125 °C triggers carbon–carbon homocoupling through five-membered moieties, forming short oligomers. Heating to 150 °C promotes chain growth into one-dimensional polymers with a 1.1 eV bandgap and extended π delocalization, alongside a minor fraction of cyclic trimers featuring a 1.1 eV HOMO–LUMO gap with both local and global aromaticity. The methodology also proceeds for Co-metallated precursors, confirming that indenyl coupling is also compatible for metalloporphyrins, establishing a general route to design π-extended porphyrin polymers.

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Publication Details

Journal
Research Square
Published
2026-11-10
DOI
https://doi.org/10.21203/rs.3.rs-11614027/v1
Primary Topic
Porphyrin and Phthalocyanine Chemistry
Type
preprint
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preprint

Polymerization of Porphyrins by Indenyl Coupling

Koen Lauwaet, José Ignacio Urgel, Pablo Merino, Diego Peña et al.
Research Square
Porphyrin and Phthalocyanine Chemistry
preprint

Polymerization of Porphyrins by Indenyl Coupling

Koen Lauwaet, José Ignacio Urgel, Pablo Merino, Diego Peña, Borja Cirera, Jesús Bello‐García, Tianchen Qin, Ana Barragán, Dolores Pérez, José Ignacio Martínez, Aurelio Gallardo, Ana R. Monteiro, David Écija, Alba García‐Frutos, Rubén Canales, Alberto Martínez‐Bajo
preprint en

Abstract

Abstract Porphyrin polymers merge the photophysical, electrochemical, sensory and catalytic properties of porphyrins with the processability and robustness of polymeric materials, offering versatile and synergetic platforms for optoelectronics and catalysis. Here we report an on-surface strategy for the atomically precise polymerization of porphyrins via regioselective indenyl coupling. Deposition of an indenyl-functionalized porphyrin on Au(111) and sequential annealing drives a stepwise transformation: cyclodehydrogenation at 100 °C planarizes the precursor into π-extended porphyrins, while annealing above 125 °C triggers carbon–carbon homocoupling through five-membered moieties, forming short oligomers. Heating to 150 °C promotes chain growth into one-dimensional polymers with a 1.1 eV bandgap and extended π delocalization, alongside a minor fraction of cyclic trimers featuring a 1.1 eV HOMO–LUMO gap with both local and global aromaticity. The methodology also proceeds for Co-metallated precursors, confirming that indenyl coupling is also compatible for metalloporphyrins, establishing a general route to design π-extended porphyrin polymers.

Research Square
Madrid Institute for Advanced Studies (ES), Consejo Superior de Investigaciones Científicas (ES), Universidade de Santiago de Compostela (ES), IMDEA Nanoscience (ES), Instituto de Ciencia de Materiales de Madrid (ES), Centro Singular de Investigación en Química Biológica y Materiales Moleculares (ES)
Porphyrin and Phthalocyanine Chemistry
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