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

Abstract

So far, the development of new iodoargentate-based hybrids, especially those compounds with metal complex cations, and the understanding of their structure–activity relationships have been of vital importance but full of challenges. Herein, using the in-situ-generated metal complex cations as structural directing agents, three new iodoargentate-based hybrids, namely, [Co(phen)3]Ag2PbI6 (phen = 1,10-phenanthroline; 1), [Ni(5,5-dmpy)3]Ag7I9·CH3CN (5,5-dmpy = 5,5-dimethyl-2,2-bipyridine; 2) and [Co(5,5-dmpy)3]Ag5I8 (3), have been solvothermally prepared and then structurally characterized. Compound 1 represents one new heterometallic Ag–Pb–I compound characteristic of the chain-like [Ag2PbI6]n2n− anions. Compound 2 features the straight one-dimensional (1D) [Ag7I9]n2n− anionic moieties, while compound 3 contains infrequent two types of curved [Ag5I8]n3n− anions. Optical properties reveal that the title compounds exhibit interesting semiconductor behaviors with the band gaps of 1.59–2.78 eV, which endow them with good photoelectric switching performances under the alternate light irradiations. We also present their Hirshfeld surface analyses, and the theoretical studies (band structures, density of states (DOS) and partial density of states (PDOS)).

A New 3D Iodoargentate Hybrid: Structure, Optical/Photoelectric Performance and Theoretical Research

“…This is markedly different from some iodoplumbate-based hybrid materials (e.g., [CH 3 NH 3 ]PbI 3 ), which usually performed poorly due to the long-term instabilities [38]. Under the visible light condition, the average photocurrent density reached to 0.37 µA•cm −2 (Figure 5a), which is comparable to those of some highly reactive iodoargentate-based hybrids, such as AgI(bpt), Ag 2 I 2 (phen), [Co(5,5-dmpy) 3 ]Ag 5 I 8 , [La(dpdo)(DMF) 14 ]Ag 12 I 18 (dpdo = 4,4 ′ -bipyridine N,N'-dioxide) and [Co(bipy) 3 ] 2 Ag 4 Bi 2 I 16 [21,29,35,39]. Moreover, the on/off current density of compound [H 2 -4,4 ′ -dpa]Ag 6 I 8 could be further enhanced by exposing the designed photoelectrode to the full-spectrum circumstance, with the observed photocurrent density of 1.23 µA•cm −2 (Figure 5b).…”

“…Of note, all atoms in compound 1 are located in the 4e site with one site symmetry. In the [Ag 6 I 8 ] n 2n− anionic moiety, all Ag centers adopted the tetrahedral geometries (Figure 1b), with the relevant Ag−I distances of 2.648( 8 -dimethyl-2,2 ′bipyridine) [3,5,8,12,17,20,21]. As for the I atoms, three different coordination modes exist: I(3) and I(6) atoms act as the bridging fashions; I(2), I(4), I(7) and I(8) atoms take on the µ 3 -I styles; while the I(1) and I(5) atoms are µ 4 -I manners connecting four Ag + ions.…”

[Ag4Br6] cluster-based 3D bromoargentate hybrid: crystal structure, optical/photoelectrical performance and theoretical study

“…5a). 34–37,41–45 This high value also suggested that compound 1 possessed good carrier transport and separation ability, which is a critical prerequisite for an excellent photoconductive material. Predominantly, its “on/off” switching ratio could be further enhanced when exposed to a full-spectrum light environment, with an achieved photocurrent density of 1.10 μA cm −2 (Fig.…”

“…This phenomenon is normal and commonly observed in some halogen-abundant haloargentate hybrids, such as [NH 4 ][Fe(bipy) 3 ] 2 Ag 6 Br 11 , [Co(bipy) 3 ] 2 Ag 4 Bi 2 Br 16 , [Fe(bipy) 3 ]AgBiBr 6 , [Co(5,5-dmpy) 3 ]Ag 5 I 8 , and [Zn(phen) 3 ] 2 Ag 2 Bi 2 I 12 . 16,34–37 The relative contributions of various intermolecular contacts to the Hirshfeld surface are summarized in Fig. 3d.…”

“…This finding was reasonable and may result from the more photogenerated electron–hole pairs due to the improved light intensity, which has also been reported for [Co(bipy) 3 ] 2 Ag 4 Bi 2 Br 16 , [Ni(bipy) 3 ]AgBiBr 6 , [NH 4 ][Fe(bipy) 3 ] 2 [Ag 6 Br 11 ], [Co(5,5-dmpy) 3 ]Ag 5 I 8 , and [Pb(MCP) 2 I]PbI 3 . 16,34–36,46…”