Conducting coordination polymers or metal-organic-frameworks have shown promising applications in energy storage, thermoelectrics, spintronics, and others. Among many conductive motifs, dithiolene-based frameworks in particular exhibit significant delocalization and high conductivity due to better energy match between sulfur atoms and metal centers. Appending thiolate groups to tetrathiafulvalene (TTF) to generate tetrathiafulvalene-tetrathiolate (TTFtt) enables the formation of extended coordination polymers that combine the properties of TTF with the rich electronic structures of transition metal dithiolenes. We recently discovered syntheses that enable the isolation of a series of redox congeners of capped TTFtt compounds and their facile transmetalation to group 10 metals. By applying this strategy, we were able to isolate reduced and oxidized NiTTFtt polymers. Interestingly, while the oxidized NiTTFtt is intrinsically metallic, reduced ones are typical p-type semiconductors. Furthermore, we found that the broad spectral absorption and electrically conducting nature of these TTFtt based materials enables highly efficient NIR-thermal conversion and good photo-thermal electrical (PTE) performance. To the best of our knowledge, the NiTTFtt materials represent the best single-component organic PTE materials for both p-type and n-type applications.

Metal-to-semiconductor transition and photo-thermal electrical properties in coordination polymers of Ni-tetrathiafulvalene tetrathiolate(TTFtt)

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