We describe five 1D-coordination polymers and two discrete silver clusters consisting of alkynides and picolinic carboxylates as co-ligands. In some cases, DMSO or EtOH further solvated the structural motifs. Utilising the sterically demanding tri-isopropylsilyl acetylene afforded a tridecanuclear cluster that possessed an unprecedented core with a silver center surrounded by six octahedrally arranged silver atoms.