Ten Coordination Polymers Constructed Using an Unprecedented Azamacrocyclic Octacarboxylate Ligand 1,4,8,11-Tetrazacyclododecane‑N,N′,N″,N‴‑Tetra-Methylene-Isophthalic Acid: Syntheses, Structures, and Photoluminescent Properties

Ten new coordination complexes, [Cd₃(H₂L)­(H₂O)₇]­·6H₂O (1), [Mn₃(H₂L)­(H₂O)₇]­·7H₂O (2), [Zn₃(H₂L)­(H₂O)₆]­·6H₂O (3), [Co₃(H₂L)­(H₂O)₆]­·5.75H₂O (4), [Fe₃(H₂L)­(H₂O)₈]­·6.5H₂O (5), [Co₃(H₂L)­(teta)₃]­·5H₂O (6), [Ni₄(L)­(teta)₄]­·2.5H₂O (7), [Ni₃(H₂L)­(teta)­(H₂O)₆]­·6H₂O (8), [Cd₄(L)­(teta)₄­(H₂O)₂]­·H₂O (9), and [Cu₂(H₄L)­(teta)₂]­·2H₂O (10) (H₈L = 1,4,8,11-tetrazacyclododecane-N,N′,N″,N‴-tetra-methylene-isophthalic acid and teta = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) have been synthesized. Their structures have been confirmed and further characterized by relative physical methods. Compounds 1 and 2 are isomorphous and demonstrate the identical three-dimensional (3D) (4,6)-connected nets with (6⁴·7²)­(6⁸·7⁶·8) topologies. Compounds 3–5 are isostructural and unfold 3D 4-fold interpenetrating frameworks with (4¹²·6³) topologies. Compound 6 is a 3D 2-fold interpenetrating framework with (4¹²·6³) topology. Compound 7 features a 3D 6-connected (4¹²·6³) net. Compounds 8 and 9 reveal two-dimensional (2D) layers, where hydrogen-bonding interactions further link adjacent layers together to obtain 3D supramolecular architectures. Compound 10 presents a one-dimensional ribbon. These ribbons are combined by π–π stackings to produce a 2D supramolecular layer. In addition, the fluorescent properties of H₈L and compounds 1, 3, and 9 have been explored, and the luminescent sensing properties of compounds 1 and 3 for small molecules have been studied.