Heterometal silver/copper(I) modulated thermochromism of two isostructural iodoplumbates

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

“…1‐D [Pb 2 AgX 7 ] n 2n– (X = I, Br) anions were prepared using [TM(2,2′‐bipy) 3 ] 2+ (TM = Mn, Fe, Co, Ni; 2,2′‐bipy = 2,2′‐bipyridine) as structural directing agents (SDAs). [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.…”

“…It has been observed that TM complexes can effectively prevent the recombination of the photogenerated electron and hole pairs, and promote the photocatalytic activity of hybrid halometalates. [11b], In compound 5 , the Ni(II) is coordinated by a dien strong chelating ligand and three weak MeCN ligands, and the heterometallic ternary [PbAg 2 I 6 ] n 2n– anion has a two‐dimensional network structure. The special structure feature of compound 5 is able to effectively trap the photoexcited electrons to inhibit the recombination of photoinduced electron–hole pairs and benefit to produce · O 2 – , · OH and h + reactive species.…”

“…However, only a few examples of the heterometallic iodometalates have been reported so far. The examples include 1‐D [Pb 3 Ag 10 I 22 ] 6– , [Pb 7 Ag 2 I 22 ] 6– , [Pb 2 Ag 5 I 13 ] 4– , [Pb 2 Ag 2 I 10 ] 4– , [Pb 2 AgI 7 ] 2– , [PbAgI 4 ] – chains,, and organic ligands coordinated neutral network of PbAg 2 I 4 (PPh 3 ) 2 (PPh 3 = triphenylphosphine) . Recently, in our effort in exploring heterometallic iodometalates, we had gained exciting Pb‐Ag heterometallic iodides [Pb 2 Ag 2 I 9 ] 3– and [Pb 3 Ag 10 I 22 ] 6– using lanthanide(III) complexes as counterions for the first time, and neutral networks of [(L)PbAgI 3 ] n (L = ethylenediamine, or 2‐diaminopropane) and [(tepa)PbAg 2 I 4 ] n (tepa = tetraethylenepentamine) decorated with ethylene polyamines at the Pb(II) center …”

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

“…Many works on halide complexes dealing with thermochromism describe this feature in terms of color changes and luminescent behavior [ 43 , 44 ] or by comparing crystallographic parameters by taking into account the sets of X-ray diffraction data at two or more temperatures [ 35 , 36 , 39 , 45 , 46 ]. It should also be noted that two different thermochromic mechanisms have been highlighted in the literature previously: charge transfer decrease, which can be found in iodoplumbate/iodoargentate complexes [ 43 , 44 , 47 ], as well as the contraction of lattice parameters and subtle changes in bond lengths in more structurally labile iodobismuthates [ 36 ] or heterometallic Ag/Cu modified iodoplumbates [ 48 ]. The latter explanation is more frequently mentioned.…”

Syntheses and crystal structures of two heterometallic iodoplumbates containing mixed-valence copper(I/II)

“…Attention has been focused on d 10 systems (especially the Cu + family) for their excellent photochemical and photophysical properties. It was found that the introduction of Cu + into the Pb/I skeleton can change the electronic configuration and therefore alter the luminescence properties of the parent Pb/I compound (Burns et al, 2006;Fan et al, 2006;Li et al, 2015). On the other hand, Coronado & Day (2004) have pointed out that the combination of magnetic moments and conduction electrons in one compound may give rise to a simple superposition of magnetic and conducting properties if ISSN 2053ISSN -2296 # 2017 International Union of Crystallography these are electronically independent, or to a mutual influence between these properties if they interact.…”