Polymeric Iodoargentate Hybrids Incorporating Octakis- or Heptakis-Solvated Lanthanide Complexes: Syntheses, Crystal Structures, and Photocatalysis

Yan Gao, Niannian Chen, Yiming Tian, Jiahua Zhang, and Dingxian Jia^*（贾定先）

College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, People’s Republic of China

Inorg. Chem.2021, 60, 3761--3772

New iodoargentate hybrids containing lanthanide complexes, [La(DMA)₈]Ag₉I₁₂·2H₂O (1) and [Ln(DMA)₇]₂Ag₁₆I₂₂ (Ln = Pr (2), Sm(3); DMA = N,N-dimethylacetamide), were prepared by diffusion methods using DMA-solvated lanthanide complexes as structure-directing agents. The octakis-solvated La³⁺ cation leads to formation of the 1-D nonanuclear [Ag₉I₁₂]_n^3n– polymeric anion constructed by AgI₄ tetrahedral units through edge sharing, while the heptakis-solvated Ln³⁺ (Ln = Pr, Sm) cation affords the new 1-D hexadecanuclear [Ag₁₆I₂₂]_n^6n– polymeric anion built up from AgI₄ units by both corner and edge sharing. Compounds 1–3 possess band gaps of 2.58, 2.77, and 2.74 eV, respectively, and show steady photocurrents in the range 14.2–18.0 μA under Xe light irradiation. They are photocatalytic active in the degradation of organic pollutants of crystal violet (CV) and rhodamine B (RhB) in water at room temperature. 2 and 3 perform higher photocatalytic activities than 1 in the CV degradation, which is attributed to the different photocurrent intensities. Photocatalytic mechanism investigations on compounds 2 and 3 show that h⁺ hole and ·O₂^– radical play major roles in the CV degradation, respectively.

链接：https://pubs.acs.org/doi/10.1021/acs.inorgchem.0c03528