Polymorphism of Two-Dimensional Semiconducting Coordination Polymers: Impact of a Lead-Sulfur Network on Photoconductivity

Ryohei Akiyoshi; Hiroki Shibahara; Akinori Saeki; Yuki Mori; Shogo Kawaguchi; Hirofumi Yoshikawa; Kazuyoshi Ogasawara; Daisuke Tanaka

doi:10.1002/chem.202400618

Polymorphism of Two-Dimensional Semiconducting Coordination Polymers: Impact of a Lead-Sulfur Network on Photoconductivity

Chemistry. 2024 Apr 3:e202400618. doi: 10.1002/chem.202400618. Online ahead of print.

Authors

Ryohei Akiyoshi¹, Hiroki Shibahara¹, Akinori Saeki², Yuki Mori³, Shogo Kawaguchi³, Hirofumi Yoshikawa⁴, Kazuyoshi Ogasawara¹, Daisuke Tanaka¹

Affiliations

¹ Department of Chemistry, School of Science, Kwansei Gakuin University, 1 Gakuen Uegahara, Sanda, Hyogo, 669-1330, Japan.
² Department of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka, 565-0871, Japan.
³ Japan Synchrotron Radiation Research Institute (JASRI), 1-1-1 Kouto, Sayo-cho, Sayo-gun, Hyogo, 679-5198, Japan.
⁴ Department of Nanotechnology for Suitable Energy, School of Engineering, Kwansei Gakuin University, 1 Gakuen Uegahara, Sanda, Hyogo, 669-1330, Japan.

PMID: 38570328
DOI: 10.1002/chem.202400618

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.

Keywords: coordination polymer; lead thiolate network; polymorphism; semiconductors.

Abstract

Grants and funding