Directing Boron–Phosphorus Bonds in Crystalline Solid: Oxidative Polymerization of P=B=P Monomers into 1D Chains

Woo, Katherine E.; Wang, Jian; Mark, Justin; Kovnir, Kirill

doi:10.1021/jacs.9b06803

Title: Directing Boron–Phosphorus Bonds in Crystalline Solid: Oxidative Polymerization of P=B=P Monomers into 1D Chains

Abstract

Over 20 years after the last inorganic ternary B–P compound was reported, Na₂BP₂, a new compound containing one-dimensional B–P polyanionic chains has been synthesized. Common high-temperature synthetic methods required for the direct reaction of boron and phosphorus negate the possible formation of metastable or low temperature phases. In this study, oxidative elimination was used to successfully condense 0D BP₂^3– anionic monomers found in a Na₃BP₂ precursor into unique 1D BP₂^2– chains consisting of five-member B₂P₃ rings connected by bridging P atoms in the crystal structure of Na₂BP₂. In conclusion, the synthesis was guided by in situ X-ray powder diffraction studies, which revealed the metastable nature of the products of oxidative elimination reactions. Na₂BP₂ is predicted to be an electron balanced semiconductor which was confirmed by UV–vis spectroscopy with the experimentally determined band gap of 1.1 eV.

Authors:

Woo, Katherine E. ^[1];

^[1]; Mark, Justin ^[1];

^[1]

Ames Lab. and Iowa State Univ., Ames, IA (United States)

Publication Date:: 2019-08-06

Research Org.:: Ames Lab., Ames, IA (United States)

Sponsoring Org.:: USDOE

OSTI Identifier:: 1561965

Report Number(s):: IS-J-10029
Journal ID: ISSN 0002-7863

Grant/Contract Number:: AC02-07CH11358

Resource Type:: Accepted Manuscript

Journal Name:: Journal of the American Chemical Society

Additional Journal Information:: Journal Volume: 141; Journal Issue: 33; Journal ID: ISSN 0002-7863

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Woo, Katherine E., Wang, Jian, Mark, Justin, and Kovnir, Kirill. Directing Boron–Phosphorus Bonds in Crystalline Solid: Oxidative Polymerization of P=B=P Monomers into 1D Chains.  United States: N. p., 2019. 
        Web.  doi:10.1021/jacs.9b06803.

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                    Woo, Katherine E., Wang, Jian, Mark, Justin, & Kovnir, Kirill. Directing Boron–Phosphorus Bonds in Crystalline Solid: Oxidative Polymerization of P=B=P Monomers into 1D Chains.  United States.  doi:https://doi.org/10.1021/jacs.9b06803

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                    Woo, Katherine E., Wang, Jian, Mark, Justin, and Kovnir, Kirill. Tue .  
        "Directing Boron–Phosphorus Bonds in Crystalline Solid: Oxidative Polymerization of P=B=P Monomers into 1D Chains".  United States.  doi:https://doi.org/10.1021/jacs.9b06803.  https://www.osti.gov/servlets/purl/1561965.

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@article{osti_1561965,

  title        = {Directing Boron–Phosphorus Bonds in Crystalline Solid: Oxidative Polymerization of P=B=P Monomers into 1D Chains},

  author       = {Woo, Katherine E. and Wang, Jian and Mark, Justin and Kovnir, Kirill},

  abstractNote = {Over 20 years after the last inorganic ternary B–P compound was reported, Na2BP2, a new compound containing one-dimensional B–P polyanionic chains has been synthesized. Common high-temperature synthetic methods required for the direct reaction of boron and phosphorus negate the possible formation of metastable or low temperature phases. In this study, oxidative elimination was used to successfully condense 0D BP23– anionic monomers found in a Na3BP2 precursor into unique 1D BP22– chains consisting of five-member B2P3 rings connected by bridging P atoms in the crystal structure of Na2BP2. In conclusion, the synthesis was guided by in situ X-ray powder diffraction studies, which revealed the metastable nature of the products of oxidative elimination reactions. Na2BP2 is predicted to be an electron balanced semiconductor which was confirmed by UV–vis spectroscopy with the experimentally determined band gap of 1.1 eV.},

  doi          = {10.1021/jacs.9b06803},

  journal      = {Journal of the American Chemical Society},

  number       = 33,

  volume       = 141,

  place        = {United States},

  year         = {2019},

  month        = {8}

}

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DOI: https://doi.org/10.1021/jacs.9b06803

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Works referencing / citing this record:

An unprecedented planar π-conjugated [B ₂ P ₅ ] ⁵⁻ group with ultra-large birefringence and nonlinearity: an ab initio study
journal, January 2020

Gong, Pifu; Zhang, Shengzi; Song, Gaomin
Chemical Communications, Vol. 56, Issue 4
DOI: 10.1039/c9cc07019b

Inorganic planar π-conjugated groups in nonlinear optical crystals: review and outlook
journal, January 2020

Gong, Pifu; Liu, Xiaomeng; Kang, Lei
Inorganic Chemistry Frontiers, Vol. 7, Issue 4
DOI: 10.1039/c9qi01589b

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Title: Directing Boron–Phosphorus Bonds in Crystalline Solid: Oxidative Polymerization of P=B=P Monomers into 1D Chains

Abstract

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