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Direct synthesis of a semiconductive double-helical phosphorus allotrope in a metal-organic framework

Author

Listed:
  • Sergei A. Sapchenko

    (University of Manchester)

  • Rodion V. Belosludov

    (Tohoku University)

  • Inigo J. Vitoria-Irezabal

    (University of Manchester)

  • Ivan Silva

    (Oxfordshire)

  • Xi Chen

    (University of Manchester
    China University of Petroleum (East China))

  • George F. S. Whitehead

    (University of Manchester)

  • John Maddock

    (University of Manchester)

  • Louise S. Natrajan

    (University of Manchester)

  • Meredydd Kippax-Jones

    (University of Manchester)

  • Dukula De Alwis Jayasinghe

    (University of Manchester)

  • Carlo Bawn

    (University of Manchester)

  • Daniil M. Polyukhov

    (University of Manchester)

  • Yinlin Chen

    (University of Manchester)

  • Vladimir P. Fedin

    (3 Lavrentiev Ave
    1 Pirogov Str.)

  • Sihai Yang

    (University of Manchester
    Peking University)

  • Martin Schröder

    (University of Manchester)

Abstract

There remains much ambiguity regarding the structure of red phosphorus. We report the adsorption and photo-polymerisation of P4 molecules encapsulated in an indium(III)-based metal-organic framework to afford a double-helical chain composite comprising of [P8] units. The similarity between the Raman spectrum of bulk red phosphorus and of the metal-organic framework – (P8)n adduct suggests the presence of such helical chains in the structure of amorphous red phosphorus. This provides crystallographic evidence of the structural building blocks of the red phosphorus allotrope stabilized within the pores of a metal-organic host. The (P8)n inclusion compound is an air-stable semiconductor with a band gap of 2.3 eV, which is relevant for gas detection and photo-catalysis. We demonstrate that this phosphorus adduct demonstrates a 10-fold increase in conversion in the oxidation of methyl orange dye compared with the parent metal-organic framework material.

Suggested Citation

  • Sergei A. Sapchenko & Rodion V. Belosludov & Inigo J. Vitoria-Irezabal & Ivan Silva & Xi Chen & George F. S. Whitehead & John Maddock & Louise S. Natrajan & Meredydd Kippax-Jones & Dukula De Alwis Jay, 2025. "Direct synthesis of a semiconductive double-helical phosphorus allotrope in a metal-organic framework," Nature Communications, Nature, vol. 16(1), pages 1-9, December.
    • Handle: RePEc:nat:natcom:v:16:y:2025:i:1:d:10.1038_s41467-025-55999-4
    DOI: 10.1038/s41467-025-55999-4
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    References listed on IDEAS

    as
    1. Andreas E. Seitz & Felix Hippauf & Werner Kremer & Stefan Kaskel & Manfred Scheer, 2018. "Facile storage and release of white phosphorus and yellow arsenic," Nature Communications, Nature, vol. 9(1), pages 1-6, December.
    2. Yasuhide Inokuma & Shota Yoshioka & Junko Ariyoshi & Tatsuhiko Arai & Yuki Hitora & Kentaro Takada & Shigeki Matsunaga & Kari Rissanen & Makoto Fujita, 2013. "X-ray analysis on the nanogram to microgram scale using porous complexes," Nature, Nature, vol. 495(7442), pages 461-466, March.
    3. Ryotaro Matsuda & Ryo Kitaura & Susumu Kitagawa & Yoshiki Kubota & Rodion V. Belosludov & Tatsuo C. Kobayashi & Hirotoshi Sakamoto & Takashi Chiba & Masaki Takata & Yoshiyuki Kawazoe & Yoshimi Mita, 2005. "Highly controlled acetylene accommodation in a metal–organic microporous material," Nature, Nature, vol. 436(7048), pages 238-241, July.
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