Heterometallic Pb–Ag Iodides from 1‐D Chains to 2‐D Layers Induced by Transition Metal Complex Cations: Syntheses, Crystal Structures, and Photocatalytic Properties

Abstract

Novel heterometallic Pb-Ag iodides [TM(en) 3 ]PbAgI 5 [TM = Mn (1), Fe (2), Zn (3)], [Ni(en) 2 ]PbAg 2 I 6 (4) (en = ethylenediamine), and [Ni(dien)(MeCN) 3 ]Pb 3 Ag 2 I 10 ·MeCN (5) (dien = diethylenetriamine) were prepared using TM(II) (TM = Mn, Fe, Zn, Ni) complex cations as structure directing agents under different conditions. In compounds 1-3, one AgI 4 tetrahedron and one PbI 6 octahedron are connected via edge-sharing into the ternary heterometallic 1-D polymeric anion [PbAgI 5 ] n 2n-

Facile syntheses, structures and photocatalytic properties of 3D iodoargentate frameworks derived from TM-flexible-amino-ligand templates

“…1a and b, the Co 2+ and Fe 2+ ions are coordinated by three en ligands to form octahedral complex cations with axial N–TM–N angles of 171.6(4)° for [Co(en) 3 ] 2+ , and 170.2(4)° for [Fe(en) 3 ] 2+ . The bond lengths of Co–N [2.169(6) Å] and Fe–N [2.214(6) Å] (Tables S2 and S3†) are consistent with the corresponding lengths of the reported [Co(en) 3 ] 2+ and [Fe(en) 3 ] 2+ complexes, 42,43 respectively. The asymmetric structural unit of the [Ag 2 I 4 ] n 2 n − anion is composed of one crystallographically independent Ag + and two I − ions (Fig.…”

Two [Co(bipy)3]3+-Templated Silver Halobismuthate Hybrids: Syntheses, Structures, Photocurrent Responses, and Theoretical Studies

“…Compared to alkali metal ions and organic amines, metal complex cations (e.g., [Fe­(bipy) 3 ] 2+ , [Ni­(phen) 3 ] 2+ ) hold great promises and have received increasing attention in recent years. − Many studies have shown that most of them are optically sensitive, whose introduction not only can result in novel structures but also may trigger some interesting physicochemical properties. This has been successfully demonstrated by some silver haloplumbates, such as [Fe­(phen) 3 ]­Ag 2 PbBr 6 , [Fe­(bipy) 3 ]­AgPb 2 Br 7 , [Mn­(en) 3 ]­AgPbI 5 , [Ni­(phen) 3 ]­Ag 2 PbI 6 , [Fe­(phen) 3 ]­Ag 2 PbI 7 , [Fe­(phen) 3 ] 2 Ag 3 Pb 2 I 11 , and [Ni­(bipy) 3 ]­AgPb 2 I 7 . − In particular, compound [Ni­(bipy) 3 ]­AgPb 2 I 7 features the unique 1D [AgPb 2 I 7 ] n 2 n – anionic chains, displaying the visible light-responding photocatalytic properties for the degradation of organic dyes . By contrast, the heterometallic halobismuthates with a transition metal complex cation were rarely established, with limited instances including [Fe­(bipy) 3 ]­AgBiI 6 , [Ni­(bipy) 3 ]­AgBiI 6 , [Fe­(bipy) 3 ]­AgBiBr 6 and [Ni­(bipy) 3 ]­AgBiBr 6 from our group …”

Three Iodoargentate-Based Hybrids Decorated by Metal Complexes: Structures, Optical/Photoelectric Properties and Theoretical Studies

“…This indicates that the title compounds are potential visible light responsive semiconductors. In addition, these band values are very consistent with their respective crystal colors and match well with those of some reported Ag-based metal halide analogues, e.g., K[Fe(bipy) 3 ] 2 Ag 6 I 11 (1.66 eV), K[Co(bipy) 3 ] 2 Ag 6 I 11 (1.75 eV), [Fe(phen) 3 ] 2 Ag 3 I 7 (1.78 eV), [NH 4 ][Fe(bipy) 3 ] 2 Ag 6 Br 11 (1.90 eV), [Ni(bipy) 3 ]AgPb 2 I 7 (1.92 eV), [Co(bipy) 3 ]Ag 3 I 6 (2.03 eV), [Ni(5,5-dmbpy) 3 ] 2 Ag 4.9 I 8.9 ·4H 2 O (2.07 eV), [(Me) 2 -DABCO] 2 Ag 5 Pb 2 I 13 (2.33 eV), [Ni(dien)(MeCN) 3 ]Ag 2 Pb 3 I 10 ·MeCN (2.42 eV), [V(DMSO) 5 (H 2 O)]Ag 6 I 8 (2.61 eV), [Ni(phen) 3 ]Ag 2 I 4 ·3DMF (2.64 eV) and [Co(phen) 3 ] 2 Ag 11 I 15 ·H 2 O (2.84 eV) [ 9 , 13 , 15 , 17 , 18 , 22 , 28 , 31 , 32 , 33 , 34 ].…”