LAUSR

Aryl propiolic acids are introduced as a new class of monomers in the field of on‐surface chemistry to build up poly(arylenebutadiynylenes) through decarboxylative Glaser coupling. As compared to aryl alkynes that are routinely used in the on‐surface Glaser coupling, it is found that the decarboxylative coupling occurs at slightly lower temperature and with excellent selectivity. Activation occurs through decarboxylation for the propiolic acids, whereas the classical Glaser coupling is achieved through alkyne CH activation, and this process shows poor selectivity. The efficiency of the decarboxylative coupling is documented by the successful polymerization of bis(propiolic acids) as monomers. It is also found that the new activation mode is compatible with aryl bromide functionalities, which allows the formation of unsymmetric metal‐organic polymers on the surface by chemoselective sequential reactions. All transformations are analyzed by a scanning tunneling microscope and are further studied by density functional theory calculations.