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. 2024 Sep 5;29(17):4217.
doi: 10.3390/molecules29174217.

1D Lead Bromide Hybrids Directed by Complex Cations: Syntheses, Structures, Optical and Photocatalytic Properties

Affiliations

1D Lead Bromide Hybrids Directed by Complex Cations: Syntheses, Structures, Optical and Photocatalytic Properties

Ya-Qi Liu et al. Molecules. .

Abstract

This study presents the synthesis, structural characterization, and evaluation of the photocatalytic performance of two novel one-dimensional (1D) lead(II) bromide hybrids, [Co(2,2'-bpy)3][Pb2Br6CH3OH] (1) and [Fe(2,2'-bpy)3][Pb2Br6] (2), synthesized via solvothermal reactions. These compounds incorporate transition metal complex cations as structural directors, contributing to the unique photophysical and photocatalytic properties of the resulting materials. Single-crystal X-ray diffraction analysis reveals that both compounds crystallize in monoclinic space groups with distinct 1D lead bromide chain configurations influenced by the nature of the complex cations. Optical property assessments show band gaps of 3.04 eV and 2.02 eV for compounds 1 and 2, respectively, indicating their potential for visible light absorption. Photocurrent measurements indicate a significantly higher electron-hole separation efficiency in compound 2, correlated with its narrower band gap. Additionally, photocatalytic evaluations demonstrate that while both compounds degrade organic dyes effectively, compound 2 also exhibits notable hydrogen evolution activity under visible light, a property not observed in 1. These findings highlight the role of metal complex cations in tuning the electronic and structural properties of lead(II) bromide hybrids, enhancing their applicability in photocatalytic and optoelectronic devices.

Keywords: hydrogen evolution reaction; organic–inorganic hybrid materials; photocatalytic activity; photocurrent response; single-crystal structure; transition metal complex cation.

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Conflict of interest statement

The authors declare no conflicts of interest.

Figures

Figure 1
Figure 1
The crystal structures of the compounds 1 and 2. (a) The 1D [Pb2Br6MeOH]2− chain of 1. (b) The 1D [Pb2Br6]2− chain of 2. (c) The packing diagram of compound 1 along the b axis. (d) The packing diagram of compound 2 along the a axis. Hydrogen atoms were omitted for clarity. Color code: Pb, gray; Br, plum; Co, orange; Fe, olive; N; blue; O, red; C, light gray. Symmetry code: 1 2 − x, 2 − y, 1 − z; 2 2 − x, 1 − y, 1 − z, 3 −1 + x, y, z; 4 1 + x, y, z.
Figure 2
Figure 2
(a) UV-vis absorption spectra of 1 (orange) and 2 (olive). (b) Excitation (short wavelength region) and emission (long wavelength region) spectra at room temperature for 1 (orange) and 2 (olive).
Figure 3
Figure 3
The photocurrent density of 1 (orange) and 2 (olive) under a xenon lamp mimicking sunlight. The curve of 1 is translated along the vertical axis to avoid overlapping.
Figure 4
Figure 4
Time-dependent absorption spectra (a,b), the linear relationship of ln(C0/C) with reaction time (c), and the recyclability (d) of the photodegradation reactions of RhB solutions over compounds 1 and 2. The solid lines in subfigure (c) are the fitting results using the equation ln(C0/C) = kt.
Figure 5
Figure 5
(a) Plots of photocatalytic hydrogen production versus time for compounds 1 (orange) and 2 in ascorbic acid solutions with different pH values. (b) Initial rates (μmol g−1 h−1) of photocatalytic hydrogen evolution for 2 at different pH values.

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