Polymeric heterometallic Pb–Ag iodometallates, iodoplumbates and iodoargentates with lanthanide complex cations as templates

Abstract

Heterometallic Pb-Ag iodometallates [Ln(DMF)8]2Pb3Ag10I22 [Ln = Ce(1), Pr(2)] were prepared by the reactions of PbI2, AgNO3 and KI in dimethylformamide (DMF) templated by [Ln(DMF)8](3+) complexes formed in situ by stirring LnCl3 in DMF. The same reactions in the absence of AgNO3 or PbI2 afforded iodoplumbate [Pr(DMF)9]2[Pr(DMF)8]Pb11I31 (3), and iodoargentates [Ln(DMF)8]Ag6I9 [Ln = Ce(4), Pr(5)], respectively. Compounds 1 and 2 contain a ternary one-dimensional polymeric [Pb3Ag10I22](6-) anion self-assembled from five AgI4, one PbI6 and one PbI4 primary units via edge- and face-sharing. Twelve PbI6 octahedra are interlinked via sharing of common faces to generate a 1D zigzag [Pb11I31(9-)]n chain in 3, which represents a new member of iodoplumbate aggregates. In 4 and 5, three AgI4 tetrahedra connect through common edges to form the [Ag6I12](6-) building block. The [Ag6I12](6-) blocks are further interlinked by sharing common edges, resulting in the 1D [Ag6I9(3-)]n chain. Optical absorption spectra showed that the synthesized Ag-iodoplumbate and iodoplumbate have potential for being used as semiconductors. Our results show that heterometallic halometallate properties can be tuned by combining structural units with different symmetries, enabling the synthesis of specific functional materials.

A Series of Iodoargentates Directed by Solvated Metal Cations Featuring Uptake and Photocatalytic Degradation of Organic Dye Pollutants

“…Connection betweent hese two blocks is ensured by Ag-I bonds and each buildingb lock is connected with two other same units to form a1 Di norganic [Ag 6 I 9 ]c hain ( Figure 1c). It should be noted that although the similar composition of 1D [Ag 6 I 9 ] 3À chains has been reported in [Ln(DMF) 8 ][Ag 6 I 9 ]( Ln = Ce, Pr), [44] {[Er(DMF) 8 ][Ag 6 I 9 ] [45] and[ Y(DMF) 8 ][Ag 6 I 9 ], [46] they feature structural characteristics distinct from those of compound 1.F e 3 + ions are solvated withs ix DMSO molecules, forming [Fe(DMSO) 6 ] 3 + cationst oa ct as counterions for the anionic iodometallate chains. As far as we know,i odoargentatesd irected by solvatedF e III cations have never been reported, in spite of some published works on iodoargentates templated by [Fe(2,2'-bipy) 3 ] 3 + or [Fe(1,10-phen) 3 ] 3 + complex.…”

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

“…The Pb 2+ ion is coordinated to six iodine anions at distances in the range of 3.1704(14)–3.3973(15) Å in 1 , forming a distorted octahedral PbI 6 PBU with equatorial and axial I–Pb–I angles in the range of 84.13(4)–101.24(4)°, and 171.35(4)–176.28(4)° in 1 , respectively. The Ag–I and Pb–I bond lengths are in the range of those observed in iodoargentates and iodoplumbates, respectively , , . The PbI 6 PBUs are inter‐connected into a linear [PbI 4 ] n chain via sharing common edges (Figure b).…”

“…[11b] 1‐D [Ag 2 Pb 2 I 9 ] n 3n– and [Pb 3 Ag 10 I 22 ] n 6n– anions were obtained with lanthanide(III) cationic SDAs of [Ln(DMSO) 8 ] 3+ (DMSO = dimethyl sulfoxide) and [Ln(DMF) 8 ] 3+ (DMF = N,N‐dimethylformamide), respectively. [13a], [13b] Now new heterometallic halides [PbAgI 5 ] n 2n– and [PbAg 2 I 6 ] n 2n– were prepared using TM complexes with ethylene polyamine ligands as SDAs.…”

Solvothermal Synthesis, Crystal Structures, and Photocatalytic Properties of Iodoplumbate Hybrids with Nickel(II) Complex Templates

“…Chen synthesized a new 1‐D iodoplumbate polymer [(Nd 2 (DMF) 12 IN 2 )(Pb 8 I 20 )] n (HIN = isonicotinic acid) using the SDA of Nd III complex formed in situ . Recently, we have prepared novel 1‐D iodoplumbate polymers [Pb 11 I 31 ] 9– and [(DMSO)Pb 4 I 11 ] n 3n– using Pr III and Ce III complex cations as SDAs . Recently, organic hybrid lead bromides have draw attention and several bromoplumbates have been reported …”