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Updated: Jun 29, 2025
Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework
Published on: April 9, 2018
Polymorphism of Two-Dimensional Semiconducting Coordination Polymers: Impact of a Lead-Sulfur Network on
Ryohei Akiyoshi1, Hiroki Shibahara1, Akinori Saeki2
1Department of Chemistry, School of Science, Kwansei Gakuin University, 1 Gakuen Uegahara, Sanda, Hyogo, 669-1330, Japan.
Abstract:
Sulfur-coordinated coordination polymers (S-CPs) have unique optoelectrical properties that originate from infinite M-S bond networks. In this study, we synthesized and characterized two polymorphs of a two-dimensional (2D) Pb(II) S-CP with a formula of [Pb(tzdt)(OAc)] (Htzdt=1,3-thiazolidine-2-thione, OAc=acetate). Our findings revealed that the thermodynamic product (KGF-26) possesses quasi-2D (-Pb-S-)n layers with weak nonbonded Pb-S bonds, whereas the kinetic product (KGF-27) has intrinsic 2D (-Pb-S-)n layers with Pb-S bonds. The results of time-resolved microwave conductivity measurements and first-principles calculations confirmed that KGF-27 exhibits higher photoconductivity than KGF-26, which establishes that the inorganic (-Pb-S-)n networks with Pb-S bonds are crucial for achieving high photoconductivity. This is the first experimental demonstration of the impact of the (-M-S-)n networks in S-CPs on photoconductivity through the comparison of crystal polymorphisms.
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