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- W4280602020 abstract "Herein, we report on the use of tetrathiavulvalene-tetrabenzoic acid, H4TTFTB, to engender semiconductivity in porous hydrogen-bonded organic frameworks (HOFs). By tuning the synthetic conditions, three different polymorphs have been obtained, denoted MUV-20a, MUV-20b, and MUV-21, all of them presenting open structures (22, 15, and 27%, respectively) and suitable TTF stacking for efficient orbital overlap. Whereas MUV-21 collapses during the activation process, MUV-20a and MUV-20b offer high stability evacuation, with a CO2 sorption capacity of 1.91 and 1.71 mmol g-1, respectively, at 10 °C and 6 bar. Interestingly, both MUV-20a and MUV-20b present a zwitterionic character with a positively charged TTF core and a negatively charged carboxylate group. First-principles calculations predict the emergence of remarkable charge transport by means of a through-space hopping mechanism fostered by an efficient TTF π-π stacking and the spontaneous formation of persistent charge carriers in the form of radical TTF•+ units. Transport measurements confirm the efficient charge transport in zwitterionic MUV-20a and MUV-20b with no need for postsynthetic treatment (e.g., electrochemical oxidation or doping), demonstrating the semiconductor nature of these HOFs with record experimental conductivities of 6.07 × 10-7 (MUV-20a) and 1.35 × 10-6 S cm-1 (MUV-20b)." @default.
- W4280602020 created "2022-05-22" @default.
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- W4280602020 date "2022-05-16" @default.
- W4280602020 modified "2023-10-15" @default.
- W4280602020 title "Semiconductor Porous Hydrogen-Bonded Organic Frameworks Based on Tetrathiafulvalene Derivatives" @default.
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- W4280602020 doi "https://doi.org/10.1021/jacs.2c01957" @default.
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