Presynthetic Redox Gated Metal-to-Insulator Transition and Photothermoelectric Properties in Nickel Tetrathiafulvalene-Tetrathiolate Coordination Polymers

Jiaze Xie; Jia-Ahn Pan; Baorui Cheng; Tengzhou Ma; Alexander S Filatov; Shrayesh N Patel; Jiwoong Park; Dmitri V Talapin; John S Anderson

doi:10.1021/jacs.2c07864

Presynthetic Redox Gated Metal-to-Insulator Transition and Photothermoelectric Properties in Nickel Tetrathiafulvalene-Tetrathiolate Coordination Polymers

J Am Chem Soc. 2022 Oct 19;144(41):19026-19037. doi: 10.1021/jacs.2c07864. Epub 2022 Oct 4.

Authors

Jiaze Xie¹, Jia-Ahn Pan¹, Baorui Cheng^{1

2}, Tengzhou Ma², Alexander S Filatov¹, Shrayesh N Patel², Jiwoong Park^{1

2}, Dmitri V Talapin^{1

2}, John S Anderson¹

Affiliations

¹ Department of Chemistry, University of Chicago, Chicago, Illinois60637, United States.
² Pritzker School of Molecular Engineering, University of Chicago, Chicago, Illinois60637, United States.

PMID: 36194683
DOI: 10.1021/jacs.2c07864

Abstract

Photothermoelectric (PTE) materials are promising candidates for solar energy harvesting and photodetection applications, especially for near-infrared (NIR) wavelengths. Although the processability and tunability of organic materials are highly advantageous, examples of organic PTE materials are comparatively rare and their PTE performance is typically limited by poor photothermal (PT) conversion. Here, we report the use of redox-active Sn complexes of tetrathiafulvalene-tetrathiolate (TTFtt) as transmetalating agents for the synthesis of presynthetically redox tuned NiTTFtt materials. Unlike the neutral material NiTTFtt, which exhibits n-type glassy-metallic conductivity, the reduced materials Li_1.2Ni_0.4[NiTTFtt] and [Li(THF)_1.5]_1.2Ni_0.4[NiTTFtt] (THF = tetrahydrofuran) display physical characteristics more consistent with p-type semiconductors. The broad spectral absorption and electrically conducting nature of these TTFtt-based materials enable highly efficient NIR-thermal conversion and good PTE performance. Furthermore, in contrast to conventional PTE composites, these NiTTFtt coordination polymers are notable as single-component PTE materials. The presynthetically tuned metal-to-insulator transition in these NiTTFtt systems directly modulates their PT and PTE properties.