An efficient strategy for the synthesis of a wide variety of coordination complexes has been developed. The synthetic protocol involves a solvothermal in situ metal ligand reaction of picolinaldehyde, ammonium acetate, and transition-metal ions, leading to the generation of 12 coordination complexes supported by a novel class of substituted 1-pyridineimidazo[1,5-a]pyridine ligands (L1-L5). The ligands L1-L5 were afforded by metal-mediated controllable conversion of the aldehyde group of picolialdehyde into a ketone and secondary, tertiary, and quaternary carbon centers, respectively. Complexes of various nuclearities were obtained: from mono-, di-, and tetranuclear to ID chain polymers. The structures of the in situ formed complexes could be controlled rationally via the choice of appropriate starting materials and tuning of the ratio of the starting materials. The plausible mechanisms for the formation of the ligands L1-L5 were proposed.