Two Silver Halobismuthate Hybrids Decorated by Photosensitive Metal Complexes: Syntheses, Structures, Photoelectric Properties, and Theoretical Studies

Abstract

Guided by photosensitive metal complexes, two new organic−inorganic hybrid silver halobismuthates, namely, [Co-(bipy) 3 ] 2 [AgBiBr 7 ][Bi 2 Br 9 ]•H 2 O (bipy = 2,2′-bipyridine, 1) and [Zn(phen) 3 ] 2 [Ag 2 Bi 2 I 12 ] (phen = 1,10-phenanthroline, 2) have been solvothermally fabricated and structurally characterized. Compound 1 is a rare [Co(bipy) 3 ] 3+ -templated Ag−Bi−X compound, featuring [AgBiBr 7 ] 3− and [Bi 2 Br 9 ] 3− as the two types of binuclear clusters. Compound 2 exhibits discrete [Ag 2 Bi 2 I 12 ] 4− anions formed by two centrosymmetric [AgBiI 8] dimers via edge-sharing. UV−vis diffuse reflection analyses showed that compounds 1 and 2 have semiconductor behaviors, with the optical absorption edges of 2.40 and 2.15 eV, respectively. Moreover, they also display excellent photoelectric switching properties, which greatly outperform or are well comparable to many halide-based counterparts, especially compound 1. The Hirshfeld surface analyses, X-ray photoelectron spectroscopy characterizations, thermal stabilities, and theoretical studies (band gaps, density of states, and wave functions) are also discussed.

A semiconductive copper iodobismuthate hybrid: structure, optical properties and photocurrent response

“…This is distinctly different from some documented metal halide counterparts ( e.g. , [NH 4 ][Fe(bipy) 3 ] 2 Ag 6 Br 11 , [Fe(phen) 3 ]Ag 2 PbBr 6 , [NH 4 ][Ni(phen) 3 ]BiI 6 , [Zn(bipy) 3 ] 2 Ag 2 BiI 6 (I) 1.355 (I 3 ) 1.645 , [Co(bipy) 3 ] 2 Ag 4 Bi 2 I 16 and [Zn(phen) 3 ] 2 Ag 2 Bi 2 I 12 ), 34–36,45,55,56 which are characteristic of large organic moieties and routinely feature the relative flat band compositions. In terms of the DOS diagram, we can see that its VB maximum was dominated by the Cu-3d and I-5p states, while the CB minimum was nearly from the Bi-6p and I-5p orbitals (Fig.…”

“…This is reasonable and may be ascribed to the more photo-generated hole/electron pairs due to the enhanced light harvesting ability, which has also appeared in the instance of [NH 4 ][Fe(bipy) 3 ] 2 Ag 6 Br 11 , [Fe(bipy) 3 ]AgBiI 6 , [Pb(MCP) 2 I]PbI 3 , [Co(bipy) 3 ] 2 [AgBiBr 7 ][Bi 2 Br 9 ]·H 2 O, [Zn(phen) 3 ] 2 [Ag 2 Bi 2 I 12 ], [Zn(bipy) 3 ] 2 Ag 2 BiI 6 (I) 1.355 (I 3 ) 1.645 and [Co(bipy) 3 ] 2 Ag 4 Bi 2 I 16 . 30,34–37,56 These behaviors displayed by compound 1 make it a new and promising semiconducting photodetector.…”

“…5a). In particular, such a value is well comparable or largely outperforms those of many high-performance halide counterparts (e. 30,[34][35][36][37]56 These behaviors displayed by compound 1 make it a new and promising semiconducting photodetector.…”

“…29 Notably, compound 1 also possesses the dispersive band distributions, in particular the CBs, indicating the strong intermolecular electronic coupling between the neighboring species. [34][35][36]45,55,56 which are characteristic of large organic moieties and routinely feature the relative flat band compositions. In terms of the DOS diagram, we can see that its VB maximum was dominated by the Cu-3d and I-5p states, while the CB minimum was nearly from the Bi-6p and I-5p orbitals (Fig.…”

Lanthanum-Centered Organotin Oxysulfide Clusters with Substitutable Coordinating Amide Solvent Molecules for Tuning Blue Light Emission

“…Although compounds 1 – 3 have the same radiative pathway and a similar luminescence mechanism, they show disparate PL intensities and PLQYs which further facilitate us to explore the cause of the differences. According to the structural analysis and theoretical calculation results, the weak interactions between clusters, directed by coordination solvent molecules with different sizes and steric effects, may play an important role for their PL performance. , Therefore, the intermolecular interactions of 1 – 3 were further evaluated by Hirschfeld surface calculations with Crystal Explorer software (Figures S18–S20). The 2D fingerprint plots demonstrate that the −S···H– interactions are much higher than the −O···H–, −N···H–, and −C···H– interactions in 1 – 3 (Figure S21).…”