4-(Pyren-1-yl)pyridine (L) with luminescence properties was self-assembled with β-diketone-based transition metal compounds to produce five new hexacoordinated metal complexes: [Zn(acac)₂L₂] (1), [Zn(hfacac)₂L₂] (2), [Ni(hfacac)₂L₂] (3), [Cu(hfacac)₂L₂] (4), and [Co(acac)₂L₂] (5) [L = 4-(pyren-1-yl)pyridine, acac = acetylacetone, and hfacac = hexafluoroacetylacetone]. The structures of these complexes were characterized by single-crystal and powder X-ray diffractometry; elemental analysis; electrospray ionization masss pectrometry; and nuclear magnetic resonance, infrared, and fluorescence spectroscopies. The β-diketone ancillary ligands and pyrenylpyridine functional ligands were bonded to Zn(II)/Ni(II) /Cu(II)/Co(II) metal ions in an O^O and two N chelating fashion, leading to the formation of mononuclear coordination complexes where one-dimensional chains and two-dimensional sheet structures were formed via π···π stacking and hydrogen bonding interactions. In addition, the solid state photoluminescence properties of these new crystalline materials were examined, with obvious differences observed between the metal complexes.