Spontaneous polymerization of benzofulvene monomers bearing a 4-Pyridylacetylene substituent in different positions of the benzofulvene scaffold

•Two benzofulvene derivatives bearing a 4-pyridylacetylene substituent in different positions (i. e. 2 and 6) of the benzofulvene scaffold are designed and synthesized.•Both benzofulvene derivatives 2-PA-BF3a and 6-PA-BF3k showed the tendency to polymerize spontaneously in the consequence of solvent removal.•NMR and MALDI-TOF studies suggested for poly-6-PA-BF3k a higher structural homogeneity with respect to poly-2-PA-BF3a.•Poly-6-PA-BF3k show an interesting hole mobility value, which was found to be around two orders of magnitude higher than that of poly(vinylcarbazole).