Three azide bridged complexes, namely, [Mn₂L₂(N₃)₄(H₂O)₂] (1), [Co₂L₂(N₃)₄]·(H₂O)₃ (2) and [Ni₂L₂(N₃)₃(H₂O)]N₃·(H₂O)₄ (3) (L = 2-morpholine-4-yl-4,6-di-pyrazol-1-yl-1,3,5-triazine), were synthesized by the reaction of L ligand, sodium azide with Mn(II), Co(II) and Ni(II) chlorides. The copper(II) chloride combined with thiocyanate and L ligand to form a mononuclear complex [CuL(CH₃OH)(SCN)(NCS)] (4). Complexes 1～4 were characterized by IR, elemental analysis and X-ray crystallographic analysis. It was worth noting that two Mn(II) atoms were connected by the end-to-end mode in 1, while Co(II) and Ni(II) atoms were connected by the end-on mode in 2 and 3. In complex 4, the central copper atom was coordinated with a sulfur atom and a nitrogen atom of the two thiocyanate ligands, respectively. Hydrogen bonds, π-π stacking interactions, thermogravimetric analysis and fluorescence properties of 1～4 were studied.