Semiconductive microporous hydrogen-bonded organophosphonic acid frameworks

Patrik Tholen Craig A. Peeples Raoul Schaper Ceyda Bayraktar Turan Erkal Mehmet Menaf Ayhan Bünyemin Çoşut Jens Beckmann A. Ozgur Yazaydin Michael Wark Gabriel Hanna Yunus Zorlu Gündoğ Yücesan

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Received Date: 12th March 20

We report a novel semiconductive, proton-conductive, microporous hydrogen-bonded organic framework derived from phenylphosphonic acid and 5,10,15,20‐tetrakis[p‐phenylphosphonic acid] porphyrin (known as GTUB5). The structure of GTUB5 was characterized using single crystal X-ray diffraction (XRD). A narrow band gap of 1.56 eV was extracted from a UV-Vis spectrum of pure GTUB5 crystals, in excellent agreement with 1.65 eV obtained from density functional theory calculations. GTUB5 was found to have a proton conductivity of 3.00 ∙ 10-6 S cm-1 at 75 °C and 75 % relative humidity. Its hexagonal voids were estimated to have a surface area of 422 m2 g-1 from grand canonical Monte Carlo simulations. GTUB5 is thermally stable under relative humidities of up to 90 % at 75 °C, as shown by XRD. These findings pave the way for a new family of microporous, proton-conductive organic semiconductors with high surface areas and high thermal stabilities.

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