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

Ten new coordination complexes, [Cd<sub>3</sub>(H<sub>2</sub>L)­(H<sub>2</sub>O)<sub>7</sub>]­·6H<sub>2</sub>O (<b>1</b>), [Mn<sub>3</sub>(H<sub>2</sub>L)­(H<sub>2</sub>O)<sub>7</sub>]­·7H<sub>2</sub>O (<b>2</b>), [Zn<sub>3</sub>(H<sub>2</sub>L)­(H<sub>2</sub>O)<sub>6</sub>]­·6H<sub>2</sub>O (<b>3</b>), [Co<sub>3</sub>(H<sub>2</sub>L)­(H<sub>2</sub>O)<sub>6</sub>]­·5.75H<sub>2</sub>O (<b>4</b>), [Fe<sub>3</sub>(H<sub>2</sub>L)­(H<sub>2</sub>O)<sub>8</sub>]­·6.5H<sub>2</sub>O (<b>5</b>), [Co<sub>3</sub>(H<sub>2</sub>L)­(teta)<sub>3</sub>]­·5H<sub>2</sub>O (<b>6</b>), [Ni<sub>4</sub>(L)­(teta)<sub>4</sub>]­·2.5H<sub>2</sub>O (<b>7</b>), [Ni<sub>3</sub>(H<sub>2</sub>L)­(teta)­(H<sub>2</sub>O)<sub>6</sub>]­·6H<sub>2</sub>O (<b>8</b>), [Cd<sub>4</sub>(L)­(teta)<sub>4</sub>­(H<sub>2</sub>O)<sub>2</sub>]­·H<sub>2</sub>O (<b>9</b>), and [Cu<sub>2</sub>(H<sub>4</sub>L)­(teta)<sub>2</sub>]­·2H<sub>2</sub>O (<b>10</b>) (H<sub>8</sub>L = 1,4,8,11-tetrazacyclododecane-<i>N</i>,<i>N</i>′,<i>N</i>″,<i>N</i>‴-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 <b>1</b> and <b>2</b> are isomorphous and demonstrate the identical three-dimensional (3D) (4,6)-connected nets with (6<sup>4</sup>·7<sup>2</sup>)­(6<sup>8</sup>·7<sup>6</sup>·8) topologies. Compounds <b>3</b>–<b>5</b> are isostructural and unfold 3D 4-fold interpenetrating frameworks with (4<sup>12</sup>·6<sup>3</sup>) topologies. Compound <b>6</b> is a 3D 2-fold interpenetrating framework with (4<sup>12</sup>·6<sup>3</sup>) topology. Compound <b>7</b> features a 3D 6-connected (4<sup>12</sup>·6<sup>3</sup>) net. Compounds <b>8</b> and <b>9</b> reveal two-dimensional (2D) layers, where hydrogen-bonding interactions further link adjacent layers together to obtain 3D supramolecular architectures. Compound <b>10</b> 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 H<sub>8</sub>L and compounds <b>1</b>, <b>3</b>, and <b>9</b> have been explored, and the luminescent sensing properties of compounds <b>1</b> and <b>3</b> for small molecules have been studied.