RT Journal Article
T1 Surface‐Assisted Synthesis of N‐Containing π‐Conjugated Polymers
A1 Sánchez-Grande, Ana
A1 Urgel, José
A1 García Benito, Inés
A1 Santos Barahona, José Manuel
A1 Biswas, Kalyan
A1 Lauwaet, Koen
A1 Gallego, José M.
A1 Rosen, Johanna
A1 Miranda, Rodolfo
A1 Björk, Jonas
A1 Martín León, Nazario
A1 Écija, David
AB On‐surface synthesis has recently emerged as a powerful strategy to design conjugated polymers previously precluded in conventional solution chemistry. Here, an N‐containing pentacene‐based precursor (tetraazapentacene) is ex‐professo synthesized endowed with terminal dibromomethylene (:CBr<jats:sub>2</jats:sub>) groups to steer homocoupling via dehalogenation on metallic supports. Combined scanning probe microscopy investigations complemented by theoretical calculations reveal how the substrate selection drives different reaction mechanisms. On Ag(111) the dissociation of bromine atoms at room temperature triggers the homocoupling of tetraazapentacene units together with the binding of silver adatoms to the nitrogen atoms of the monomers giving rise to a N‐containing conjugated coordination polymer (P1). Subsequently, P1undergoes ladderization at 200 °C, affording a pyrrolopyrrole‐bridged conjugated polymer (P2). On Au(111) the formation of the intermediate polymer P1 is not observed and, instead, after annealing at 100 °C, the conjugated ladder polymer P2 is obtained, revealing the crucial role of metal adatoms on Ag(111) as compared to Au(111). Finally, on Ag(100) the loss of :CBr2 groups affords the formation of tetraazapentacene monomers, which coexist with polymer P1. Our results contribute to introduce protocols for the synthesis of N‐containing conjugated polymers, illustrating the selective role of the metallic support in the underlying reaction mechanisms.</jats:p>
PB Wiley
SN 2198-3844
YR 2022
FD 2022
LK https://hdl.handle.net/20.500.14352/93405
UL https://hdl.handle.net/20.500.14352/93405
LA spa
NO A. Sánchez-Grande, J. I. Urgel, I. García-Benito, J. Santos, K. Biswas, K. Lauwaet, J. M. Gallego, J. Rosen, R. Miranda, J. Björk, N. Martín, D. Écija, Surface-Assisted Synthesis of N-Containing π-Conjugated Polymers. Adv. Sci. 2022, 9, 2200407. https://doi.org/10.1002/advs.202200407
NO European Commission
NO Comunidad de Madrid
NO Ministerio de Ciencia e Innovación (España)
NO Ministerio de Economía y Competitividad (España)
DS Docta Complutense
RD 9 abr 2025