In virtue of the cationic tri(pyridin-4-yl)amine (TPA) derivatives acting as the templates, two iodometallates, [Me₃HTPA]₂[CuI₃][Cu₁₀I₁₆] (1) and [Me₃TPA][Ag₅I₈] (2), were constructed with different architectures. Compound 1 features a discrete [Cu₁₀I₁₆]^6– cluster, which is further combined with [CuI₃]^2– and two [Me₃HTPA]⁴⁺ moieties through electrostatic interactions to result in a 3D supramolecular framework. Two types of infinite Ag–I chains with different orientations are formed in iodoargentate 2, and adjacent chains, together with in situ N-methylated cations, are further aggregated into a final 3D supramolecule. The syntheses, crystal structures, and optical properties have been studied. Notably, compound 1 displays efficient visible-light-driven photocatalytic performance for the degradation of dye pollutants. The catalytic mechanism was investigated through radical trapping experiments as well as theoretical calculations. Moreover, both the iodocuprate and iodoargentate hybrids exhibit second harmonic generation (SHG) effects, which are comparable to and even better than that of KH₂PO₄, indicating that the iodometallate hybrids templated by TPA-based cations could potentially serve as new candidates for second-order nonlinear optics (NLO) materials.

中文翻译：

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具有光催化活性和二次谐波生成效率的碘钙酸盐和碘银酸盐的模板合成


以阳离子三（吡啶-4-基）胺 （TPA） 衍生物为模板，构建了两种碘金属酸盐，[Me₃HTPA]₂[CuI₃][Cu₁₀I₁₆] （1） 和 [Me₃TPA][Ag₅I₈] （2），具有不同的结构。化合物 1 具有一个离散的 [Cu₁₀I₁₆]^6– 簇，通过静电相互作用进一步与 [CuI₃] ^2– 和两个 [Me₃HTPA]⁴⁺ 部分结合，形成 3D 超分子框架。在碘炳酸盐 2 中形成两种具有不同取向的无限 Ag-I 链，相邻链与原位 N-甲基化阳离子一起进一步聚集成最终的 3D 超分子。已经研究了合成、晶体结构和光学性质。值得注意的是，化合物 1 对染料污染物的降解表现出有效的可见光驱动光催化性能。通过自由基捕获实验和理论计算研究了催化机制。此外，碘首相酸盐和碘银酸盐杂化物都表现出二次谐波产生 （SHG） 效应，与 KH₂PO₄ 相当甚至更好，这表明由 TPA 基阳离子模板化的碘金属酸盐杂化物有可能成为二阶非线性光学 （NLO） 材料的新候选物。