Machine-Learning-Assisted Selective Synthesis of a Semiconductive Silver Thiolate Coordination Polymer with Segregated Paths for Holes and Electrons

Takuma Wakiya; Yoshinobu Kamakura; Hiroki Shibahara; Kazuyoshi Ogasawara; Akinori Saeki; Ryosuke Nishikubo; Akihiro Inokuchi; Hirofumi Yoshikawa; Daisuke Tanaka

doi:10.1002/anie.202110629

Machine-Learning-Assisted Selective Synthesis of a Semiconductive Silver Thiolate Coordination Polymer with Segregated Paths for Holes and Electrons

Angew Chem Int Ed Engl. 2021 Oct 18;60(43):23217-23224. doi: 10.1002/anie.202110629. Epub 2021 Sep 24.

Authors

Takuma Wakiya¹, Yoshinobu Kamakura¹, Hiroki Shibahara¹, Kazuyoshi Ogasawara¹, Akinori Saeki², Ryosuke Nishikubo², Akihiro Inokuchi³, Hirofumi Yoshikawa⁴, Daisuke Tanaka^{1

5}

Affiliations

¹ Department of Chemistry, School of Science and Technology, Kwansei Gakuin University, 2-1 Gakuen, Sanda, Hyogo, 669-1337, Japan.
² Department of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka, 565-0871, Japan.
³ Department of Informatics, School of Science and Technology, Kwansei Gakuin University, 2-1 Gakuen, Sanda, Hyogo, 669-1337, Japan.
⁴ Department of Nanotechnology for Sustainable Energy, School of Science and Technology, Kwansei Gakuin University, 2-1 Gakuen, Sanda, Hyogo, 669-1337, Japan.
⁵ JST PRESTO, 2-1 Gakuen, Sanda, Hyogo, 669-1337, Japan.

PMID: 34431599
DOI: 10.1002/anie.202110629

Abstract

Coordination polymers (CPs) with infinite metal-sulfur bond networks have unique electrical conductivities and optical properties. However, the development of new (-M-S-)_n -structured CPs is hindered by difficulties with their crystallization. Herein, we describe the use of machine learning to optimize the synthesis of trithiocyanuric acid (H₃ ttc)-based semiconductive CPs with infinite Ag-S bond networks, report three CP crystal structures, and reveal that isomer selectivity is mainly determined by proton concentration in the reaction medium. One of the CPs, [Ag₂ Httc]_n , features a 3D-extended infinite Ag-S bond network with 1D columns of stacked triazine rings, which, according to first-principle calculations, provide separate paths for holes and electrons. Time-resolved microwave conductivity experiments show that [Ag₂ Httc]_n is highly photoconductive (φΣμ_max =1.6×10^-4 cm² V^-1 s^-1 ). Thus, our method promotes the discovery of novel CPs with selective topologies that are difficult to crystallize.

Keywords: coordination polymers; crystal engineering; machine learning; semiconductors; silver thiolate networks.

Abstract

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