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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 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.

Authors:
 [1]; ORCiD logo [1];  [1]; ORCiD logo [1]
  1. Ames Lab. and Iowa State Univ., Ames, IA (United States)
Publication Date:
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.
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. https://doi.org/10.1021/jacs.9b06803
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. https://doi.org/10.1021/jacs.9b06803. https://www.osti.gov/servlets/purl/1561965.
@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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Cited by: 3 works
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Figures / Tables:

Figure 1 Figure 1: Top: Statistics for structurally characterized compounds containing at least one B–P covalent bond. Bottom: Examples of molecular B-P clusters.1b,1c B: green; P: orange; C: grey, H atoms are omitted for clarity.

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Works referenced in this record:

The Cambridge Structural Database
journal, April 2016

  • Groom, Colin R.; Bruno, Ian J.; Lightfoot, Matthew P.
  • Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials, Vol. 72, Issue 2, p. 171-179
  • DOI: 10.1107/S2052520616003954

Novel Boron-Phosphorus Cages with C4B4P4 and C2B4P4 Frameworks
journal, March 1988

  • Driess, Matthias; Pritzkow, Hans; Siebert, Walter
  • Angewandte Chemie International Edition in English, Vol. 27, Issue 3
  • DOI: 10.1002/anie.198803991

Phosphane-borane chemistry. Open-chain and cyclic phosphane-boranes based on tetramethyldiphosphane
journal, September 1989

  • Schmidbaur, Hubert; Wimmer, Thomas; Grohmann, Andreas
  • Chemische Berichte, Vol. 122, Issue 9
  • DOI: 10.1002/cber.19891220902

Boron-Phosphorus Compounds and Multiple Bonding
journal, May 1990

  • Power, Philip P.
  • Angewandte Chemie International Edition in English, Vol. 29, Issue 5
  • DOI: 10.1002/anie.199004491

Boron Phosphide, a III–V Compound of Zinc-Blende Structure
journal, May 1957


The Firstcloso-Diphosphahexaborne, P2B4Cl4
journal, July 1988

  • Haubold, Wolfgang; Keller, Willi; Sawitzki, Gisela
  • Angewandte Chemie International Edition in English, Vol. 27, Issue 7
  • DOI: 10.1002/anie.198809251

Crystal and molecular structure of phosphorus trifluoride- tris(difluoroboryl)borane, B4F6-PF3
journal, April 1969

  • DeBoer, Barry G.; Zalkin, Allan; Templeton, David H.
  • Inorganic Chemistry, Vol. 8, Issue 4
  • DOI: 10.1021/ic50074a028

[BP2]3⊖ and[BAs2]3⊖, Zintl Anions with Propadiene Structure
journal, January 1990

  • von Schnering, Hans-Georg; Somer, Mehmet; Hartweg, Martin
  • Angewandte Chemie International Edition in English, Vol. 29, Issue 1
  • DOI: 10.1002/anie.199000651

Crystal structure of caesium diphosphidoborate, Cs 3 (BP 2 )
journal, February 1990


Crystal structure of sodium diphosphidoborate, Na 3 (BP 2 )
journal, February 1990


Crystal structure of potassium diphosphidoborate, K 3 BP 2
journal, February 1990


Crystal structures of trirubidium diarsenidoborate, Rb3BAs2 and trirubidium diphosphidoborate, Rb3BP2
journal, January 1995

  • Somer, M.; Carrillo-Cabrera, W.; Peters, E. -M.
  • Zeitschrift für Kristallographie - Crystalline Materials, Vol. 210, Issue 10
  • DOI: 10.1524/zkri.1995.210.10.779

Magnetism and Negative Magnetoresistance of Two Magnetically Ordering, Rare-Earth-Containing Zintl phases with a New Structure Type: EuGa 2 Pn 2 (Pn = P, As)
journal, August 2009

  • Goforth, Andrea M.; Hope, Håkon; Condron, Cathie L.
  • Chemistry of Materials, Vol. 21, Issue 19
  • DOI: 10.1021/cm901219u

Synthesis, Crystal and Electronic Structures of the New Zintl phases Ba 3 Al 3 Pn 5 ( Pn = P, As) and Ba 3 Ga 3 P 5
journal, December 2012

  • He, Hua; Tyson, Chauntae; Saito, Maia
  • Inorganic Chemistry, Vol. 52, Issue 1
  • DOI: 10.1021/ic302437t

Flux Growth and Electronic Properties of Ba 2 In 5 Pn 5 (Pn = P, As): Zintl Phases Exhibiting Metallic Behavior
journal, September 2008

  • Mathieu, Josiah; Achey, Randall; Park, Ju-Hyun
  • Chemistry of Materials, Vol. 20, Issue 17
  • DOI: 10.1021/cm8015353

Mineralization Routes to Polyphosphides: Cu 2 P 20 and Cu 5 InP 16
journal, June 2008

  • Lange, Stefan; Bawohl, Melanie; Weihrich, Richard
  • Angewandte Chemie International Edition, Vol. 47, Issue 30
  • DOI: 10.1002/anie.200705540

The Metal Flux: A Preparative Tool for the Exploration of Intermetallic Compounds
journal, November 2005

  • Kanatzidis, Mercouri G.; Pöttgen, Rainer; Jeitschko, Wolfgang
  • Angewandte Chemie International Edition, Vol. 44, Issue 43
  • DOI: 10.1002/anie.200462170

Thermoelectric and magnetic properties of rare earth borides: Boron cluster and layered compounds
journal, July 2019


Synthesis and Characterization of Single-Phase Metal Dodecaboride Solid Solutions: Zr 1– x Y x B 12 and Zr 1– x U x B 12
journal, May 2019

  • Akopov, Georgiy; Mak, Wai H.; Koumoulis, Dimitrios
  • Journal of the American Chemical Society, Vol. 141, Issue 22
  • DOI: 10.1021/jacs.9b03482

A Simple, General Synthetic Route toward Nanoscale Transition Metal Borides
journal, February 2018

  • Jothi, Palani R.; Yubuta, Kunio; Fokwa, Boniface P. T.
  • Advanced Materials, Vol. 30, Issue 14
  • DOI: 10.1002/adma.201704181

A Hydride Route to Ternary Alkali Metal Borides: A Case Study of Lithium Nickel Borides
journal, February 2019

  • Gvozdetskyi, Volodymyr; Hanrahan, Michael P.; Ribeiro, Raquel A.
  • Chemistry – A European Journal, Vol. 25, Issue 16
  • DOI: 10.1002/chem.201805398

Computationally Driven Discovery of a Family of Layered LiNiB Polymorphs
journal, September 2019

  • Gvozdetskyi, Volodymyr; Bhaskar, Gourab; Batuk, Maria
  • Angewandte Chemie International Edition, Vol. 58, Issue 44
  • DOI: 10.1002/anie.201907499

First-Principles Determination of Ultrahigh Thermal Conductivity of Boron Arsenide: A Competitor for Diamond?
journal, July 2013


Clathrate Structure of Silicon Na8Si46 and NaxSi136 (x < 11)
journal, December 1965


Preparation and Crystal Growth of Na 24 Si 136
journal, July 2009

  • Beekman, Matt; Baitinger, Michael; Borrmann, Horst
  • Journal of the American Chemical Society, Vol. 131, Issue 28
  • DOI: 10.1021/ja903362b

A guest-free germanium clathrate
journal, September 2006

  • Guloy, Arnold M.; Ramlau, Reiner; Tang, Zhongjia
  • Nature, Vol. 443, Issue 7109
  • DOI: 10.1038/nature05145

On the clathrate form of elemental silicon, Si136: preparation and characterisation of NaxSi136 (x→0)
journal, May 2004


X-Ray Investigations of the Ternary System Fe-P-B. Some Features of the Systems Cr-P-B, Mn-P-B, Co-P-B and Ni-P-B.
journal, January 1962


Chemistry and structural chemistry of phosphides and polyphosphides. 48. Bridging chasms with polyphosphides
journal, January 1988

  • Von Schnering, Hans Georg; Hoenle, Wolfgang
  • Chemical Reviews, Vol. 88, Issue 1
  • DOI: 10.1021/cr00083a012

Breaking the Tetra-Coordinated Framework Rule: New Clathrate Ba 8 M 24 P 28+ δ ( M =Cu/Zn)
journal, January 2017

  • Dolyniuk, Juli-Anna; Zaikina, Julia V.; Kaseman, Derrick C.
  • Angewandte Chemie International Edition, Vol. 56, Issue 9
  • DOI: 10.1002/anie.201611510

High-pressure synthesis and structural characterization of three new polyphosphides, α-SrP3, BaP8, and LaP5
journal, July 2003


The Smaller the Better: Hosting Trivalent Rare-Earth Guests in Cu–P Clathrate Cages
journal, June 2018


Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


Structure validation in chemical crystallography
journal, January 2009

  • Spek, Anthony L.
  • Acta Crystallographica Section D Biological Crystallography, Vol. 65, Issue 2, p. 148-155
  • DOI: 10.1107/S090744490804362X

Ba 2 Si 3 P 6 : 1D Nonlinear Optical Material with Thermal Barrier Chains
journal, July 2019

  • Mark, Justin; Wang, Jian; Wu, Kui
  • Journal of the American Chemical Society, Vol. 141, Issue 30
  • DOI: 10.1021/jacs.9b04653

The Main Group Macrocycle [{(PCH2CH2PAlMe2)2}4]⋅4 [AlMe3]
journal, May 2001


B 8 S 16 -An “Inorganic Porphine”
journal, June 1980

  • Krebs, Bernt; Hürter, Hans-Ulrich
  • Angewandte Chemie International Edition in English, Vol. 19, Issue 6
  • DOI: 10.1002/anie.198004811

Facile Conversion of Red Phosphorus into Soluble Polyphosphide Anions by Reaction with Potassium Ethoxide
journal, March 2016

  • Dragulescu‐Andrasi, Alina; Miller, L. Zane; Chen, Banghao
  • Angewandte Chemie International Edition, Vol. 55, Issue 12
  • DOI: 10.1002/anie.201511186

Early-Transition-Metal-Mediated Activation and Transformation of White Phosphorus
journal, July 2010

  • Cossairt, Brandi M.; Piro, Nicholas A.; Cummins, Christopher C.
  • Chemical Reviews, Vol. 110, Issue 7
  • DOI: 10.1021/cr9003709

A Carbon-Free Sandwich Complex [(P5)2Ti]2-
journal, February 2002


Phosphorus Nanorods—Two Allotropic Modifications of a Long-Known Element
journal, August 2004

  • Pfitzner, Arno; Bräu, Michael F.; Zweck, Josef
  • Angewandte Chemie International Edition, Vol. 43, Issue 32
  • DOI: 10.1002/anie.200460244

Fibrous Red Phosphorus
journal, November 2005

  • Ruck, Michael; Hoppe, Diana; Wahl, Bernhard
  • Angewandte Chemie International Edition, Vol. 44, Issue 46
  • DOI: 10.1002/anie.200503017

The Extended Stability Range of Phosphorus Allotropes
journal, September 2014

  • Bachhuber, Frederik; von Appen, Jörg; Dronskowski, Richard
  • Angewandte Chemie International Edition, Vol. 53, Issue 43
  • DOI: 10.1002/anie.201404147

Electron Localization in Solid-State Structures of the Elements: the Diamond Structure
journal, February 1992

  • Savin, Andreas; Jepsen, Ove; Flad, Jürgen
  • Angewandte Chemie International Edition in English, Vol. 31, Issue 2
  • DOI: 10.1002/anie.199201871

ELF: The Electron Localization Function
journal, September 1997

  • Savin, Andreas; Nesper, Reinhard; Wengert, Steffen
  • Angewandte Chemie International Edition in English, Vol. 36, Issue 17
  • DOI: 10.1002/anie.199718081

BaAu 2 P 4 : Layered Zintl Polyphosphide with Infinite 1 ( P ) Chains
journal, June 2013

  • Fulmer, James; Kaseman, Derrick C.; Dolyniuk, Juli-Anna
  • Inorganic Chemistry, Vol. 52, Issue 12
  • DOI: 10.1021/ic400584w

Twisted Kelvin Cells and Truncated Octahedral Cages in the Crystal Structures of Unconventional Clathrates, AM 2 P 4 (A = Sr, Ba; M = Cu, Ni)
journal, June 2015


Inorganic Double Helices in Semiconducting SnIP
journal, September 2016

  • Pfister, Daniela; Schäfer, Konrad; Ott, Claudia
  • Advanced Materials, Vol. 28, Issue 44
  • DOI: 10.1002/adma.201603135

Flexible and Ultrasoft Inorganic 1D Semiconductor and Heterostructure Systems Based on SnIP
journal, February 2019

  • Ott, Claudia; Reiter, Felix; Baumgartner, Maximilian
  • Advanced Functional Materials, Vol. 29, Issue 18
  • DOI: 10.1002/adfm.201900233

Few-Layer GeAs Field-Effect Transistors and Infrared Photodetectors
journal, April 2018


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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