Issue 6, 2024

Impact of substituent position on crystal structure and photoconductivity in 1D and 2D lead(ii) benzenethiolate coordination polymers

Abstract

Coordination polymers containing a sulfur coordination atom (S-CPs) are an emerging class of materials with unique optoelectronic properties resulting from their inorganic metal–sulfur (–M–S–)n networks. Although the structural dimensionalities of (–M–S–)n networks govern the semiconductive properties of S-CPs, few systematic investigations have examined the impact of these dimensionalities on their semiconductive nature. In this study, we explored the relationship between the (–Pb–S–)n dimensionality and photoconductivity. We systematically synthesized Pb(II) S-CPs with the formula [Pb(x-SPhOMe)2] (x = ortho (KGF-32), meta (KGF-33), and para (KGF-34); HSPhOMe = methoxybenzenthiol). Single-crystal X-ray diffraction showed that KGF-32 and KGF-34 featured holodirected coordination spheres, but 1D (–Pb–S–)n chains with [PbO2S4] octahedra and 2D (–Pb–S–)n layers with [PbS6] octahedra, respectively. In contrast, KGF-33 features a 1D (–Pb–S–)n chain comprising a hemidirected [PbS5] coordination sphere. Notably, time-resolved microwave conductivity measurements and first-principles calculations revealed that the 2D-extended (–Pb–S–)n layer with the holodirected [PbS6] octahedron observed in KGF-34 served as a pathway for electron mobility. The findings of this study provide further design strategies for fabricating highly photoconductive Pb(II) S-CPs.

Graphical abstract: Impact of substituent position on crystal structure and photoconductivity in 1D and 2D lead(ii) benzenethiolate coordination polymers

Supplementary files

Article information

Article type
Paper
Submitted
26 Nov 2023
Accepted
25 Dec 2023
First published
29 Dec 2023

J. Mater. Chem. C, 2024,12, 1958-1964

Impact of substituent position on crystal structure and photoconductivity in 1D and 2D lead(II) benzenethiolate coordination polymers

R. Akiyoshi, A. Saeki, K. Ogasawara and D. Tanaka, J. Mater. Chem. C, 2024, 12, 1958 DOI: 10.1039/D3TC04362B

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