Two novel compounds [Zn(bip)(BDC)](1) and [Co(bip) 2 Cl 2 · 4H 2 O] (2) [bip = 2-(4-bromophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline, BDC = phthalate acid] have been synthesized by hydrothermal reactions and characterized by elemental analysis, thermogravimetric (TG) analysis, infrared spectrum (IR), and single-crystal X-ray diffraction. Single-crystal X-ray diffraction reveals that compounds 1 and 2 are zero-dimensional (0D) architecture, and the existence of hydrogen bonds and π -π interactions lead the 0D to 2D novel frameworks. Hydrogen bonds and π -π interactions are powerful interactions for directing supramolecular architectures. TG analysis shows clear courses of weight loss, which corresponds to the decomposition of different ligands. The luminescent properties for the ligand bip and compounds 1-2 are also discussed.