<p>The palladium-catalyzed heteroarylation of tris(2-aminoethyl)amine (TREN) and tris(3-aminopropyl)amine (TRPN) with isomeric bromoquinolines was studied. The yields of the target <i>N,N′,N″</i>-tri(quinolinyl) derivatives were shown to strongly depend on both the structure of branched polyamines and the position of the bromine atom in quinolines. The best results (over 70% product yields) were achieved in the reactions of 6- and 8-bromoquinolines with TRPN, with further optimization increasing the yield of the 6-quinolinyl derivative up to 96%. Also, using the reactions of TREN and TRPN with 6-bromoquinoline, the successful application of catalysis by non-immobilized nanoparticles and the copper-containing coordination polymer HKUST-1 was demonstrated, with the formation of the target <i>N,N′,N″</i>-tri(quinolin-6-yl) derivatives in yields over 90%. The possibility of obtaining macrocycles was exemplified by the reaction of 3,3′-dibromobiphenyl with TRPN and its monodansylated derivative under Pd⁰ catalysis; more complex macrocycles containing TRPN and oxadiamine moieties along with a fluorophore group (quinoline or dansyl) were synthesized. The absorption and fluorescence spectra of the obtained compounds were studied in the presence of metal salts and the observed characteristic changes of these spectra in the presence of Zn^II and Cu^II ions suggest macrocyclic TRPN derivatives to be promising optical sensors for these cations.</p>