Controlling the thermoelectric properties of organo-metallic coordination polymers through backbone geometry

Zilu Liu, Md Azimul Haque, Chris N Savory, Tianjun Liu, Satoru Matsuishi, Oliver Fenwick, David O. Scanlon, Martijn A. Zwijnenburg, Derya Baran*, Bob C. Schroeder*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

2 Scopus citations

Abstract

Poly(nickel-benzene-1,2,4,5-tetrakis(thiolate)) (Ni-btt), an organometallic coordination polymer (OMCP) characterized by the coordination between benzene-1,2,4,5-tetrakis(thiolate) (btt) and Ni2+ ions, has been recognized as a promising p-type thermoelectric material. In this study, we employed a constitutional isomer based on benzene-1,2,3,4-tetrakis(thiolate) (ibtt) to generate the corresponding isomeric polymer, poly(nickel-benzene-1,2,3,4-tetrakis(thiolate)) (Ni-ibtt). Comparative analysis of Ni-ibtt and Ni-btt reveals several common infrared (IR) and Raman features attributed to their similar square-planar nickel-sulfur (Ni-S) coordination. Nevertheless, these two polymer isomers exhibit substantially different backbone geometries. Ni-btt possesses a linear backbone, whereas Ni-ibtt exhibits a more undulating, zig-zag-like structure. Consequently, Ni-ibtt demonstrates slightly higher solubility and an increased bandgap in comparison to Ni-btt. The most noteworthy dissimilarity, however, manifests in their thermoelectric properties. While Ni-btt exhibits p-type behavior, Ni-ibtt demonstrates n-type carrier characteristics. This intriguing divergence prompted further investigation into the influence of OMCP backbone geometry on the electronic structure and, particularly, the thermoelectric properties of these materials.

Original languageEnglish (US)
Pages (from-to)377-389
Number of pages13
JournalFaraday Discussions
Volume250
DOIs
StateAccepted/In press - 2023

Bibliographical note

Publisher Copyright:
© 2023 The Royal Society of Chemistry.

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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