[SMe₃]₂[Bi₂Ag₂I₁₀], a silver iodido bismuthate with an unusually small band gap

Abstract

The synthesis and characterization of a new silver iodido bismuthate with a low optical band gap highlights the decisive role of building unit connectivity for the optical properties in this class of materials.

Optical Properties and Metal‐Dependent Charge Transfer in Iodido Pentelates

“…In both cases this is well in line with what is found for other compounds featuring the same anionic motif measured at similar temperatures. [18][19][20] The anions are surrounded by pyrazinium cations, which are interconnected via hydrogen bonding with co-crystallized water (see Figure 1A/B). Although, it was not possible to reliably locate the hydrogen position in the electron density map, we assume that each pyrazine moiety is singly protonated, as this fits the overall charge.…”

Copper- and Silver-Containing Heterometallic Iodobismuthates: Features of Thermochromic Behavior

“…Through direct comparison of various related copper- and silver-containing iodobismuthates ( Figure 5 and Figure S1 in Supplementary Materials ) of different structural types, we can conclude that, as a rule, the band gap of Cu-containing substances is lower than that of silver iodobismuthates, except for (SMe 3 ) 2 [Ag 2 Bi 2 I 10 ] with an unusually small (1.82 eV) band gap [ 27 ]. The mean E g value (at room temperature) calculated for Bi/Cu iodometallates 1 – 4 is lower than for Ag-containing hybrids 5 – 9 (1.85 vs. 1.97 eV), and these values are in a very good agreement with previously published data for polymeric (Et 4 N) 2 [Cu 2 Bi 2 I 10 ] (1.89 eV [ 25 ]), (Et 4 N) 2 [Cu 2 Bi 2 I 10 ] (2.05 eV [ 26 ]), as well as for discrete [PPh 4 ] 4 [Cu 2 Bi 2 I 12 ] and [PPh 4 ] 4 [Ag 2 Bi 2 I 12 ] (1.8 vs. 2.1 eV [ 19 ]) heterometallic compounds.…”

“… Overview of one-dimensional anions of copper and silver iodobismuthates and their band gaps in eV taken from literature (Feldmann, 2001 [ 20 ]; Chai, 2007 [ 25 ]; Chai, 2007 [ 26 ]; Möbs, 2020 [ 28 ], Möbs, 2022 [ 27 ]; Shentseva, 2022 [ 41 ], Shentseva, 2022 [ 42 ]). In compound from [ 20 ] ( top left ), the band gap for copper iodobismuthate was not provided.…”

“…Amongst the wide variety in the studied materials, prepared through various approaches, one promising method for altering electronic properties and developing new materials should be particularly emphasized: the combination of p - and d -elements ( d -elements typically being copper and silver) in the anion. According to this strategy, heterometallic copper- and silver-containing iodobismuthates with zero-dimensional [ 19 , 20 , 21 , 22 , 23 , 24 ], one-dimensional [ 20 , 25 , 26 , 27 , 28 ] ( Figure S1 ) or two-dimensional [ 29 , 30 ] anionic motifs have been characterized previously. However, the overall number of known heterometallic iodometallates remains lower than that of homometallic ones, but this trend can change, as recent works clearly demonstrate [ 27 , 31 , 32 , 33 , 34 ].…”

“…According to this strategy, heterometallic copper- and silver-containing iodobismuthates with zero-dimensional [ 19 , 20 , 21 , 22 , 23 , 24 ], one-dimensional [ 20 , 25 , 26 , 27 , 28 ] ( Figure S1 ) or two-dimensional [ 29 , 30 ] anionic motifs have been characterized previously. However, the overall number of known heterometallic iodometallates remains lower than that of homometallic ones, but this trend can change, as recent works clearly demonstrate [ 27 , 31 , 32 , 33 , 34 ].…”