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

• Published in: Journal of materials chemistry. C, Materials for optical and electronic devices Vol. 12; no. 6; pp. 1958 - 1964
• Main Authors: Akiyoshi, Ryohei, Saeki, Akinori, Ogasawara, Kazuyoshi, Tanaka, Daisuke
• Format: Journal Article
• Language: English
• Published: Cambridge Royal Society of Chemistry 08.02.2024
• Subjects: Coordination polymers; Crystal structure; Electron mobility; First principles; Optoelectronics; Photoconductivity; Single crystals; Sulfur
• ISSN: 2050-7526; 2050-7534
• DOI: 10.1039/d3tc04362b

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 [PbO 2 S 4 ] octahedra and 2D (-Pb-S-) n layers with [PbS 6 ] octahedra, respectively. In contrast, KGF-33 features a 1D (-Pb-S-) n chain comprising a hemidirected [PbS 5 ] coordination sphere. Notably, time-resolved microwave conductivity measurements and first-principles calculations revealed that the 2D-extended (-Pb-S-) n layer with the holodirected [PbS 6 ] 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. We revealed the relationship between the inorganic (-M-S-) n network and photoconductivity by systematically synthesizing semiconductive Pb( ii ) coordination polymers with methoxybenzenethiol.