Template Synthesis\nof Iodocuprate and Iodoargentate\nwith Photocatalytic Activity and Second Harmonic Generation Efficiency

In virtue of the cationic tri(pyridin-4-yl)amine (TPA)\nderivatives\nacting as the templates, two iodometallates, [Me<sub>3</sub>HTPA]<sub>2</sub>[CuI<sub>3</sub>][Cu<sub>10</sub>I<sub>16</sub>] (<b>1</b>) and [Me<sub>3</sub>TPA][Ag<sub>5</sub>I<sub>8</sub>] (<b>2</b>), were constructed with different architectures. Compound <b>1</b> features a discrete [Cu<sub>10</sub>I<sub>16</sub>]<sup>6–</sup> cluster, which is further combined with [CuI<sub>3</sub>]<sup>2–</sup> and two [Me<sub>3</sub>HTPA]<sup>4+</sup> moieties through electrostatic interactions to result in a 3D supramolecular\nframework. Two types of infinite Ag–I chains with different\norientations are formed in iodoargentate <b>2</b>, and adjacent\nchains, together with in situ <i>N</i>-methylated cations,\nare further aggregated into a final 3D supramolecule. The syntheses,\ncrystal structures, and optical properties have been studied. Notably,\ncompound <b>1</b> displays efficient visible-light-driven photocatalytic\nperformance for the degradation of dye pollutants. The catalytic mechanism\nwas investigated through radical trapping experiments as well as theoretical\ncalculations. Moreover, both the iodocuprate and iodoargentate hybrids\nexhibit second harmonic generation (SHG) effects, which are comparable\nto and even better than that of KH<sub>2</sub>PO<sub>4</sub>, indicating\nthat the iodometallate hybrids templated by TPA-based cations could\npotentially serve as new candidates for second-order nonlinear optics\n(NLO) materials.