A Low‐dimensional Viologen/Iodoargentate Hybrid [(BV)₂­(Ag₅I₉)]_n: Structure, Properties, and Theoretical Study

Abstract

A new low‐dimensional benzyl viologen/iodoargentate hybrid, [(BV)2(Ag5I9)]n (1) (BV2+ = benzyl viologen) was prepared. In 1, (Ag6I9)n2– chain exhibits a new type of one‐dimensional chain constructed from vertex‐sharing of Ag5I10 units, and its two‐dimensional layer structure was constructed from C–H···I hydrogen bonds. Strong luminescence at 404 nm can be detected in 1. DFT calculation suggests that 1 displays a reduced bandgap, which is led by a more dispersed LUMO band of BV2+ compared with MV2+ in [MV(Ag2I4)]n.

Syntheses, Crystal Structures, and Photocatalytic Properties of Polymeric Iodoargentates [TM(2,2‐bipy)3]Ag3I5 (TM = Mn, Fe, Co, Ni, Zn)

“…Compounds 2 and 4 exhibit similar green and azure‐blue emission with λ max = 524 nm and 496 nm, respectively. These luminescence properties are similar to those found for iodoargentates directed by transition metal complex cations 12,14–16. According to the results for similar hybrid iodoargentates, the emission bands can be assigned to mixtures of metal‐to‐metal transfer (Ag 5 s or 5 p ‐to‐Ag 4 d ) and iodide‐to‐metal charge transfer (I 5 p ‐to‐Ag 4 d ) affected by the metal–metal interactions; this has been investigated and validated by molecular orbital calculations for some related hybrid iodoargentates 28…”

“…The wave‐shaped α‐[Ag 5 I 7 ] 2– chain is composed of Ag 5 I 9 clusters, whereas the β‐[Ag 5 I 7 ] 2– and γ‐[Ag 5 I 7 ] 2– chains are based on the interconnection of Ag 4 I 9 units (A‐type) and AgI 4 tetrahedrons (B‐type) in A‐B‐A‐B and A‐B‐B‐A orders, respectively. The [Ag 5 I 9 ] 4– chain is relatively seldom found and is based on [Ag 5 I 10 ] 5– clusters with corner‐sharing 16. Furthermore, Jia's group reported a complex [Ag 11 I 15 ] 4– double chain formed by interconnection of 1D Ag 11 I 16 single chains 14b…”

“…More interestingly, the tetrahedral AgI 4 unit features strong self‐assembly characteristics and diversiform condensation modes including corner‐, edge‐, and face‐sharing, as well as short Ag ··· Ag interactions, termed argentophilicity 7–20. To date, many silver iodide anions with the general formula (Ag m I n ) ( n – m )– have been synthesized and structurally characterized, such as zero‐dimensional (0D) [Ag 4 I 8 ] 4– , [Ag 5 I 9 ] 4– , [Ag 5 I 10 ] 5– , [Ag 6 I 12 ] 6– , and [Ag 7 I 13 ] 6– clusters,7–9 and 1D chains of [AgI 2 ] – , [Ag 4 I 6 ] 2– , [Ag 2 I 5 ] 3– , [Ag 6 I 8 ] 2– , [Ag 10 I 12 ] 2– , [Ag 5 I 7 ] 2– , [Ag 5 I 9 ] 4– , etc 10–16. Through the use of the 0D clusters and 1D chains as building blocks, some two‐dimensional (2D) layers have also been constructed and characterized, such as [Ag 2 I 3 ] – , [Ag 4 I 5 ] – , [Ag 5 I 6 ] – , [Ag 11 I 15 ] 4– , etc 17,18.…”

Hierarchical symmetry transfer and flexible charge matching in five [M(phen)3]2+directed iodoargentates with 1 to 3D frameworks

“…5b), which can also be described as adding one Ag( 1) atom into the C 3 symmetry axis of the Ag 6 I 13 building unit. 24 Especially, two nets with (10,3) topology and four-fold helical chains along the c-axis (Fig. 5c).…”

Syntheses, Crystal Structures, and Photocatalytic Properties of Bromoargentates Induced by Transition‐Metal–phen Complex Cations

“…To date, a large number of silver(I) iodine [Ag m I n ] ( n – m )– anions ranging from discrete clusters (0D) to one‐dimensional (1D) chains, two‐dimensional (2D) layers, and three‐dimensional (3D) frameworks have been reported and characterized. Examples of iodoargentate anions include the 0D clusters [Ag 4 I 8 ] 4– , [Ag 14 I 16 ] 2– , and [Ag 14 I 22 ] 8– ; the 1D chains [Ag 2 I 3 ] – , [Ag 2 I 4 ] 2– , [Ag 3 I 5 ] 2– , [Ag 4 I 6 ] 2– , [Ag 5 I 7 ] 2– , [Ag 5 I 9 ] 4– , [Ag 6 I 9 ] 3– , and [Ag 11 I 15 ] 4– ; the 2D layers [Ag 2 I 3 ] – , [Ag 4 I 5 ] – , [Ag 5 I 6 ] – , [Ag 6 I 8 ] 2– , and [Ag 6 I 9 ] 3– ;[3c], [15b], and the 3D networks [AgI 2 ] – , [Ag 2 I 4 ] 2– , [Ag 4 I 6 ] 2– , [Ag 5 I 6 ] – , [Ag 5 I 7 ] 2– , [Ag 9 I 13 ] 4– , [Ag 12 I 16 ] 4– , [Ag 13 I 17 ] 4– , and [Ag 14 I 16 ] 2– , . The structures and dimensionalities of iodoargentates are influenced by various factors, including pH value, solvent, and reaction temperature in the synthesis process and structure‐directing agents (SDAs).…”