Crystal Structure Solid-State Cross Polarization Magic Angle Spinning <sup>13</sup>C NMR Correlation in Luminescent d<sup>10</sup> Metal-Organic Frameworks Constructed with the 1,2-Bis(1,2,4-triazol-4-yl)ethane Ligand

Hydrothermal reactions of 1,2-bis(1,2,4-triazol-4-yl)ethane (btre) with copper(II), zinc(II), and cadmium(II) salts have yielded the dinuclear complexes [Zn<sub>2</sub>Cl<sub>4</sub>(μ<sub>2</sub>-btre)<sub>2</sub>] (<b>1</b>) and [Zn<sub>2</sub>Br<sub>4</sub>(μ<sub>2</sub>-btre)<sub>2</sub>] (<b>2</b>), the one-dimensional coordination polymer <sub>∞</sub><sup>1</sup>[Zn(NCS)<sub>2</sub>(μ<sub>2</sub>-btre)] (<b>3</b>), the two-dimensional networks <sub>∞</sub><sup>2</sup>[Cu<sub>2</sub>(μ<sub>2</sub>-Cl)<sub>2</sub>(μ<sub>4</sub>-btre)] (<b>4</b>), <sub>∞</sub><sup>2</sup>[Cu<sub>2</sub>(μ<sub>2</sub>-Br)<sub>2</sub>(μ<sub>4</sub>-btre)] (<b>5</b>), and <sub>∞</sub><sup>2</sup>{[Cd<sub>6</sub>(μ<sub>3</sub>-OH)<sub>2</sub>(μ<sub>3</sub>-SO<sub>4</sub>)<sub>4</sub>(μ<sub>4</sub>-btre)<sub>3</sub>(H<sub>2</sub>O)<sub>6</sub>](SO<sub>4</sub>)·∼6H<sub>2</sub>O} (<b>6</b>), and the three-dimensional frameworks <sub>∞</sub><sup>3</sup>{[Cu(μ<sub>4</sub>-btre)]ClO<sub>4</sub>·∼0.25H<sub>2</sub>O} (<b>7</b>), <sub>∞</sub><sup>3</sup>{[Zn(μ<sub>4</sub>-btre)(μ<sub>2</sub>-btre)](ClO<sub>4</sub>)<sub>2</sub>} (<b>8</b>), <sub>∞</sub><sup>3</sup>{[Cd(μ<sub>4</sub>-btre)(μ<sub>2</sub>-btre)](ClO<sub>4</sub>)<sub>2</sub>} (<b>9</b>), and <sub>∞</sub><sup>3</sup>[Cu<sub>2</sub>(μ<sub>2</sub>-CN)<sub>2</sub>(μ<sub>4</sub>-btre)] (<b>10</b>, 2-fold 3D interpenetrated framework). The copper-containing products <b>4</b>, <b>5</b>, <b>7</b>, and <b>10</b> contain the metal in the +1 oxidation state, from a simultaneous redox and self-assembly reaction of the Cu(II) starting materials. The cyanide-containing framework <b>10</b> has captured the CN<sup>−</sup> ions from the oxidative btre decomposition. The perchlorate frameworks <b>7</b>, <b>8</b>, or <b>9</b> react in an aqueous NH<sub>4</sub><sup>+</sup>PF<sub>6</sub><sup>−</sup> solution with formation of the related PF<sub>6</sub><sup>−</sup>-containing frameworks. The differences in the metal-btre bridging mode (μ<sub>2</sub>-κ<i>N</i>1:<i>N</i>1′, μ<sub>2</sub>-κ<i>N</i>1:<i>N</i>2 or μ<sub>4</sub>-κ<i>N</i>1:<i>N</i>2:<i>N</i>1′:<i>N</i>2′) and the btre ligand symmetry can be correlated with different signal patterns in the <sup>13</sup>C cross polarization magic angle spinning (CPMAS) NMR spectra. Compounds <b>2</b>, <b>4</b>, <b>5</b> and <b>7</b> to <b>10</b> exhibit fluorescence at 403−481 nm upon excitation at 270−373 nm which is not seen in the free btre ligand.