Rational Design of Stable Dianions by Functionalizing Polycyclic Aromatic Hydrocarbons

Zhong, Mingmin; Zhou, Jian; Jena, Peru

doi:10.1002/cphc.201700346

Title: Rational Design of Stable Dianions by Functionalizing Polycyclic Aromatic Hydrocarbons

Abstract

Using density functional theory, we have carried out a systematic study of the stability and electronic properties of neutral and multiply charged molecules B_nC1_0-nX₈ (n=0, 1, 2; X=H, F, CN). Our main objective is to explore if the replacements of core C atoms and/or H atoms in naphthalene (C₁₀H₈) can enhance the stability of their dianions. Indeed, we find that the dianions of BnC_10-n(CN)₈ are more stable than their monoanions with energies of 0.61 eV, 0.57 eV, and 1.97 eV for n=0, 1, 2, respectively. Furthermore, polycyclic aromatic hydrocarbons become stable as dianions only when H atoms are substituted by more electronegative species. Hence, a rational design approach by tailoring composition and ligands can lead to a new class of organic molecules that are capable of carrying multiple charges.

Authors:

Zhong, Mingmin ^[1]; Zhou, Jian ^[2]; Jena, Peru ^[2]

Southwest Univ., Chongqing (China); Virginia Commonwealth Univ., Richmond, VA (United States)
Virginia Commonwealth Univ., Richmond, VA (United States)

Publication Date:: Mon May 08 00:00:00 EDT 2017

Research Org.:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC) Center (NERSC).

Sponsoring Org.:: USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division

OSTI Identifier:: 1461656

Grant/Contract Number:: FG02-96ER45579; AC02-05CH11231

Resource Type:: Accepted Manuscript

Journal Name:: ChemPhysChem

Additional Journal Information:: Journal Volume: 18; Journal Issue: 14; Journal ID: ISSN 1439-4235

Publisher:: ChemPubSoc Europe

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 25 ENERGY STORAGE; density functional calculations; dianions; lithium-ion batteries; multiply charged clusters; polycyclic aromatic hydrocarbons

Citation Formats


                    Zhong, Mingmin, Zhou, Jian, and Jena, Peru. Rational Design of Stable Dianions by Functionalizing Polycyclic Aromatic Hydrocarbons.  United States: N. p., 2017. 
Web.  doi:10.1002/cphc.201700346.

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                    Zhong, Mingmin, Zhou, Jian, & Jena, Peru. Rational Design of Stable Dianions by Functionalizing Polycyclic Aromatic Hydrocarbons.  United States.  https://doi.org/10.1002/cphc.201700346

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                    Zhong, Mingmin, Zhou, Jian, and Jena, Peru. Mon .  
"Rational Design of Stable Dianions by Functionalizing Polycyclic Aromatic Hydrocarbons".  United States.  https://doi.org/10.1002/cphc.201700346.  https://www.osti.gov/servlets/purl/1461656.

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@article{osti_1461656,

  title        = {Rational Design of Stable Dianions by Functionalizing Polycyclic Aromatic Hydrocarbons},

  author       = {Zhong, Mingmin and Zhou, Jian and Jena, Peru},

  abstractNote = {Using density functional theory, we have carried out a systematic study of the stability and electronic properties of neutral and multiply charged molecules BnC10-nX8 (n=0, 1, 2; X=H, F, CN). Our main objective is to explore if the replacements of core C atoms and/or H atoms in naphthalene (C10H8) can enhance the stability of their dianions. Indeed, we find that the dianions of BnC10-n(CN)8 are more stable than their monoanions with energies of 0.61 eV, 0.57 eV, and 1.97 eV for n=0, 1, 2, respectively. Furthermore, polycyclic aromatic hydrocarbons become stable as dianions only when H atoms are substituted by more electronegative species. Hence, a rational design approach by tailoring composition and ligands can lead to a new class of organic molecules that are capable of carrying multiple charges.},

  doi          = {10.1002/cphc.201700346},

  journal      = {ChemPhysChem},

  number       = 14,

  volume       = 18,

  place        = {United States},

  year         = {Mon May 08 00:00:00 EDT 2017},

  month        = {Mon May 08 00:00:00 EDT 2017}

}

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https://doi.org/10.1002/cphc.201700346

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Cited by: 3 works

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Figure 1: The most stable structures of B_nC_10-nX₈ ($n$ = 0, 1, 2; X = H, F, CN). 0/−/2− represent the neutral, monoanion and dianion, respectively.

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Title: Rational Design of Stable Dianions by Functionalizing Polycyclic Aromatic Hydrocarbons

Abstract

Citation Formats

Figures / Tables:

Ab Initio Study of the Hypercloso Boron Hydrides B n H n and B n H n - . Exceptional Stability of Neutral B 13 H 13 journal, May 2000

Density‐functional thermochemistry. III. The role of exact exchange journal, April 1993

Electron transmission study of the temporary negative ion states of selected benzenoid and conjugated aromatic hydrocarbons journal, January 1987

Stability of B 12 (CN) 12 2− : Implications for Lithium and Magnesium Ion Batteries journal, February 2016

Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density journal, January 1988

Gas-Phase Stability of Derivatives of the c loso -Hexaborate Dianion B 6 H 6 2- journal, May 2002

Big Is Beautiful−“Aromaticity” Revisited from the Viewpoint of Macromolecular and Supramolecular Benzene Chemistry journal, May 2001

Extension of Electron Affinities and Ionization Potentials of Aromatic Hydrocarbons journal, October 1966

Electron Affinities of Polycyclic Aromatic Hydrocarbons journal, January 2001

The Delocalization Index as an Electronic Aromaticity Criterion: Application to a Series of Planar Polycyclic Aromatic Hydrocarbons journal, January 2003

Dianionic Tetraborates Do Exist as Stable Entities journal, September 2002

Substituent-Stabilized Organic Dianions in the Gas Phase and Their Potential Use as Electrolytes in Lithium-Ion Batteries journal, July 2016

An Efficient Halogen-Free Electrolyte for Use in Rechargeable Magnesium Batteries journal, May 2015

Unparalleled lithium and sodium superionic conduction in solid electrolytes with large monovalent cage-like anions journal, January 2015

Self‐consistent molecular orbital methods 25. Supplementary functions for Gaussian basis sets journal, April 1984

Quantentheoretische Beitr�ge zum Benzolproblem: I. Die Elektronenkonfiguration des Benzols und verwandter Verbindungen journal, March 1931

Calculation of Electron Affinities of Polycyclic Aromatic Hydrocarbons and Solvation Energies of Their Radical Anion journal, November 2006

Organic Superhalogens journal, July 2014

Stability of B 12 (CN) 12 2− : Implications for Lithium and Magnesium Ion Batteries journal, February 2016

Superhalogens as Building Blocks of Halogen-Free Electrolytes in Lithium-Ion Batteries journal, October 2014

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B 12 (SCN) 12 – : An Ultrastable Weakly Coordinating Dianion journal, March 2017

Remarkable electron accepting properties of the simplest benzenoid cyanocarbons: hexacyanobenzene, octacyanonaphthalene and decacyanoanthracene journal, January 2006

An Efficient Halogen-Free Electrolyte for Use in Rechargeable Magnesium Batteries journal, May 2015

Reaction Intermediates during the Dehydrogenation of Metal Borohydrides: A Cluster Perspective journal, September 2010

A benchmark theoretical study of the electron affinities of benzene and linear acenes journal, August 2008

Theoretical estimation of the maximal value of the first, second and higher electron affinity of chemical compounds journal, March 1990

Ab Initio Study of the Hypercloso Boron Hydrides B _n H _n and B _n H _n ^- . Exceptional Stability of Neutral B ₁₃ H ₁₃
journal, May 2000

Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993

Electron transmission study of the temporary negative ion states of selected benzenoid and conjugated aromatic hydrocarbons
journal, January 1987

Stability of B ₁₂ (CN) ₁₂ ²⁻ : Implications for Lithium and Magnesium Ion Batteries
journal, February 2016

Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
journal, January 1988

Gas-Phase Stability of Derivatives of the c loso -Hexaborate Dianion B ₆ H ₆ ^2-
journal, May 2002

Big Is Beautiful−“Aromaticity” Revisited from the Viewpoint of Macromolecular and Supramolecular Benzene Chemistry
journal, May 2001

Extension of Electron Affinities and Ionization Potentials of Aromatic Hydrocarbons
journal, October 1966

Electron Affinities of Polycyclic Aromatic Hydrocarbons
journal, January 2001

The Delocalization Index as an Electronic Aromaticity Criterion: Application to a Series of Planar Polycyclic Aromatic Hydrocarbons
journal, January 2003

Dianionic Tetraborates Do Exist as Stable Entities
journal, September 2002

Substituent-Stabilized Organic Dianions in the Gas Phase and Their Potential Use as Electrolytes in Lithium-Ion Batteries
journal, July 2016

An Efficient Halogen-Free Electrolyte for Use in Rechargeable Magnesium Batteries
journal, May 2015

Unparalleled lithium and sodium superionic conduction in solid electrolytes with large monovalent cage-like anions
journal, January 2015

Self‐consistent molecular orbital methods 25. Supplementary functions for Gaussian basis sets
journal, April 1984

Quantentheoretische Beitr�ge zum Benzolproblem: I. Die Elektronenkonfiguration des Benzols und verwandter Verbindungen
journal, March 1931

Calculation of Electron Affinities of Polycyclic Aromatic Hydrocarbons and Solvation Energies of Their Radical Anion
journal, November 2006

Organic Superhalogens
journal, July 2014

Stability of B ₁₂ (CN) ₁₂ ²⁻ : Implications for Lithium and Magnesium Ion Batteries
journal, February 2016

Superhalogens as Building Blocks of Halogen-Free Electrolytes in Lithium-Ion Batteries
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Superhalogens as Building Blocks of Halogen-Free Electrolytes in Lithium-Ion Batteries
journal, October 2014

B ₁₂ (SCN) ₁₂ ^– : An Ultrastable Weakly Coordinating Dianion
journal, March 2017

Remarkable electron accepting properties of the simplest benzenoid cyanocarbons: hexacyanobenzene, octacyanonaphthalene and decacyanoanthracene
journal, January 2006

An Efficient Halogen-Free Electrolyte for Use in Rechargeable Magnesium Batteries
journal, May 2015

Reaction Intermediates during the Dehydrogenation of Metal Borohydrides: A Cluster Perspective
journal, September 2010

A benchmark theoretical study of the electron affinities of benzene and linear acenes
journal, August 2008

Theoretical estimation of the maximal value of the first, second and higher electron affinity of chemical compounds
journal, March 1990