The coordination of Zn(II), Ag(I), Cu(II), Cu(I) and Co(II) salts with N,N,N′,N′-tetrakis(4-pyridyl)-1,4-phenylenediamine (L) generated seven novel supramolecular coordination assemblies, {[Cu^I₆L₃Cl₆]·3MeCN}_n (1), {[Cu^I₂LCl₂]·2DMSO}_n (2), {[Cu^ILI]}_n (3), {[Zn₂L(HCOO)₄]}_n (4), {[Ag₄L₂(N₃)₄]·2H₂O}_n (5), {[Co₄L₂(SO₄)₄(H₂O)₁₂]·2CH₃CN}_n (6) and {[CuL(CH₃COO)₂(H₂O)₂]·2MeOH}_n (7). In complexes 1 and 2, the Cu(II) atoms have been converted to Cu(I). Complexes 1, 4 and 5 show 1D or 2D coordination structures, and all of them are further linked by π⋯π stacking interactions to afford 3D structures. Complex 2 has a 2D structure composed of Cu₂Cl₂ units and L ligands. Complex 3 exhibits a doubly interpenetrated 3D structure. In complex 6, the 2D coordination networks are further linked by hydrogen bonds to afford a 3D supramolecular structure. Similar to complex 6, the 1D chains in complex 7 are assembled into a 2D network through hydrogen bonds. Based on the novel structures, the solid state luminescent properties of the complexes were investigated and discussed.