Construction of a Ag<sub>12</sub> High-Nuclearity Metallamacrocyclic 3D Framework

An unprecedented high-nuclearity metallamacrocycle-based 3D silver framework with formula {[Ag<sub>2</sub>(C<sub>25</sub>H<sub>27</sub>N<sub>6</sub>O)<sub>2</sub>](CH<sub>3</sub>OH)(H<sub>2</sub>O)<sub>0.17</sub>}<sub><i>n</i></sub> (<b>1</b>), built on the basis of dodecanuclear silver building blocks, has been synthesized and characterized, and it shows strong phosphorescence emission at 10 K, which is a consequence of the presence of intersystem crossing from singlet to triplet caused by the heavy-atom effect of silver ions.