The recent discover of the multifaceted emissive features of triimidazo[1,2-a:1',2'-c:1'',2''-e][1,3,5]triazine (cyclic triimidazole) which displays crystallization-induced and mechanochromic emission, together with room temperature ultralong phosphorescence (RTUP) under ambient conditions has highlighted the potentiality of this simple organic molecule [1]. In view of possible applications in Organic Light Emitting Diodes or in fields such as sensing or bioimaging [2], the cyclic scaffold has been functionalized by introduction of the pyridine moiety, a versatile ligand with peculiar properties which opens up also to the fields of pharmaceuticals, catalysis, material science and supramolecular chemistry [3].  Starting from 3-bromotriimidazo[1,2-a:1',2'-c:1'',2''-e][1,3,5]triazine (1), the cyclic triimidazole derivative (2) functionalized with 2-pyridine has been successfully obtained by Stille coupling, while (3), bearing a 4-pyridine substituent, was prepared in high yields by Suzuki–Miyaura reaction. Powder of 2 displays room temperature phosphorescence, for compound 3 phosphorescence was observed only at 77K. The complete spectroscopical characterization together with a structural investigation to elucidate the structure/properties relationships will be here presented.