Polymerization of Polyanthrylene on a Titanium Dioxide (011)‐(2×1) Surface

Abstract

On‐surface polymerization is feasible on semiconducting surfaces. Thermally triggered covalent coupling of 10,10′‐dibromo‐9,9′‐bianthryl molecules on the TiO2(011)‐(2×1) surface is demonstrated. The result paves the way for application of the thermally driven on‐surface polymerization on semiconducting surfaces and indicates that methods based on such a reaction are more universal than previously thought.

Ordering of Zn-centered porphyrin and phthalocyanine on TiO2(011): STM studies

“…The characteristic zig-zag rows of the protruding oxygen atoms extending along the [01−1] crystallographic direction are clearly visible both on the model drawing (light red balls) and at the high-resolution empty state STM image [29–32]. The additional bright corrugations seen on top of the reconstruction rows (seen in the STM image but not incorporated in the model) correspond to hydroxy groups [11,16]. …”

“…In the context of adsorption studies, it is important to note that the (110) face of rutile usually contains numerous oxygen vacancies, often filled with hydroxy groups [13]. Those common surface defects are known to have an important effect on the molecule migration and surface diffusion barriers for Pd atoms [14–15], and as demonstrated by Kolmer et al, on the TiO 2 (011)-(2×1) surface, they play a very significant role in on-surface synthesis of polymers [16–17]. In the present work we use a TiO 2 (011)-(2×1) surface, since from our previous reports [5,12,18–22] we know that this rutile face offers higher mobility for molecular building blocks than the (110) one.…”

On‐Surface Synthesis of Atomically Precise Graphene Nanoribbons

“…Alternatively, one may consider devising a strategy for the direct synthesis on the surface of a semiconductor or insulator. In this case, the catalytic role of the metal needs to be taken over by other mechanisms, such as the interaction with surface hydroxyl groups in the polymerization of aryl halides on the rutile TiO 2 (011) surface [ 72,73 ] or the excitation by UV light in laser-induced polymerization of DBBA on mica. [ 74 ] While this alternative route seems promising, the corresponding efforts are still at an early stage.…”

On-surface polymerization on a semiconducting oxide: aryl halide coupling controlled by surface hydroxyl groups on rutile TiO2(011)

“…11 In this process, proton transfer from the surface hydroxyl group to an adsorbed precursor molecule leads to an activated monomer, which may couple with another, non-activated molecule. After C-C bond formation the proton could remain on the molecule and the process is repeated leading to the oligomerization.…”