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Title: Pancake π–π Bonding Goes Double: Unexpected 4e/All-Sites Bonding in Boron- and Nitrogen-Doped Phenalenyls

Abstract

Phenalenyl is an important neutral pi-radical due to its capability to form unconventional pancake pi-pi bonding interactions, whereas its analogues with graphitic boron (B) or nitrogen (N)-doping have been regarded as closed-shell systems and therefore received much less attention. By using high-level quantum chemistry calculations, we also show that the B- and N-doped closed-shell phenalenyls unexpectedly form open-shell singlet pi-dimers with diradicaloid character featuring 2e/all-sites double pi-pi bonding. Moreover, by proper substitutions, the doped phenalenyl derivatives can be made open-shell species that form closed shell singlet pi-dimers bound by stronger 4e/all-sites double pi-pi bonding. Moreover, covalent pi-pi bonding overlap is distributed on all of the atomic sites giving robust and genuine pancake-shaped pi-dimers which, depending on the number of electrons available in the bonding interactions, are equally or more stable than the pi-dimers of the pristine phenalenyl.

Authors:
 [1];  [2];  [3];  [2]
  1. Sichuan Univ., Chengdu (China)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  3. Chinese Academy of Sciences (CAS), Beijing (China)
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1185694
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 6; Journal Issue: 12; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Tian, Yong-Hui, Sumpter, Bobby G., Du, Shiyu, and Huang, Jingsong. Pancake π–π Bonding Goes Double: Unexpected 4e/All-Sites Bonding in Boron- and Nitrogen-Doped Phenalenyls. United States: N. p., 2015. Web. doi:10.1021/acs.jpclett.5b00857.
Tian, Yong-Hui, Sumpter, Bobby G., Du, Shiyu, & Huang, Jingsong. Pancake π–π Bonding Goes Double: Unexpected 4e/All-Sites Bonding in Boron- and Nitrogen-Doped Phenalenyls. United States. https://doi.org/10.1021/acs.jpclett.5b00857
Tian, Yong-Hui, Sumpter, Bobby G., Du, Shiyu, and Huang, Jingsong. 2015. "Pancake π–π Bonding Goes Double: Unexpected 4e/All-Sites Bonding in Boron- and Nitrogen-Doped Phenalenyls". United States. https://doi.org/10.1021/acs.jpclett.5b00857. https://www.osti.gov/servlets/purl/1185694.
@article{osti_1185694,
title = {Pancake π–π Bonding Goes Double: Unexpected 4e/All-Sites Bonding in Boron- and Nitrogen-Doped Phenalenyls},
author = {Tian, Yong-Hui and Sumpter, Bobby G. and Du, Shiyu and Huang, Jingsong},
abstractNote = {Phenalenyl is an important neutral pi-radical due to its capability to form unconventional pancake pi-pi bonding interactions, whereas its analogues with graphitic boron (B) or nitrogen (N)-doping have been regarded as closed-shell systems and therefore received much less attention. By using high-level quantum chemistry calculations, we also show that the B- and N-doped closed-shell phenalenyls unexpectedly form open-shell singlet pi-dimers with diradicaloid character featuring 2e/all-sites double pi-pi bonding. Moreover, by proper substitutions, the doped phenalenyl derivatives can be made open-shell species that form closed shell singlet pi-dimers bound by stronger 4e/all-sites double pi-pi bonding. Moreover, covalent pi-pi bonding overlap is distributed on all of the atomic sites giving robust and genuine pancake-shaped pi-dimers which, depending on the number of electrons available in the bonding interactions, are equally or more stable than the pi-dimers of the pristine phenalenyl.},
doi = {10.1021/acs.jpclett.5b00857},
url = {https://www.osti.gov/biblio/1185694}, journal = {Journal of Physical Chemistry Letters},
issn = {1948-7185},
number = 12,
volume = 6,
place = {United States},
year = {Wed Jun 03 00:00:00 EDT 2015},
month = {Wed Jun 03 00:00:00 EDT 2015}
}

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Cited by: 28 works
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Works referenced in this record:

Synthetic organic spin chemistry for structurally well-defined open-shell graphene fragments
journal, February 2011


Design of organic metals and superconductors
journal, July 1975


Aromaticity on the Pancake-Bonded Dimer of Neutral Phenalenyl Radical as Studied by MS and NMR Spectroscopies and NICS Analysis
journal, March 2006


Evidence of σ- and π-Dimerization in a Series of Phenalenyls
journal, December 2014


Comparative Analysis of the Multicenter, Long Bond in [TCNE] ·− and Phenalenyl Radical Dimers: A Unified Description of Multicenter, Long Bonds
journal, June 2009


Is There a Lower Limit to the CC Bonding Distances in Neutral Radical π-Dimers? The Case of Phenalenyl Derivatives
journal, August 2010


Charge Shift Bonding Concept in Radical π-Dimers
journal, December 2011


Double Pancake Bonds: Pushing the Limits of Strong π–π Stacking Interactions
journal, September 2014


Fine-Tuning the Single-Molecule Magnet Properties of a [Dy(III)-Radical] 2 Pair
journal, June 2013


The Tetracyanopyrazinide Dimer Dianion, [TCNP] 2 2− . 2-Electron 8-Center Bonding
journal, June 2009


Bistability and the Phase Transition in 1,3,2-Dithiazolo[4,5- b ]pyrazin-2-yl
journal, November 2004


Keys for the Existence of Stable Dimers of Bis-tetrathiafulvalene (bis-TTF)-Functionalized Molecular Clips Presenting [TTF] •+ ···[TTF] •+ Long, Multicenter Bonds at Room Temperature
journal, September 2013


Four-Center Carbon−Carbon Bonding
journal, March 2007


Synthesis, Intermolecular Interaction, and Semiconductive Behavior of a Delocalized Singlet Biradical Hydrocarbon
journal, October 2005


Resonance Balance Shift in Stacks of Delocalized Singlet Biradicals
journal, July 2009


Hybrid Density Functional Theory Studies on the Magnetic Interactions and the Weak Covalent Bonding for the Phenalenyl Radical Dimeric Pair
journal, September 2002


Heteroatom-doped graphene materials: syntheses, properties and applications
journal, January 2014


Doped graphene for metal-free catalysis
journal, January 2014


Binding Interactions in Dimers of Phenalenyl and Closed-Shell Analogues
journal, April 2013


Rotational Barrier in Phenalenyl Neutral Radical Dimer: Separating Pancake and van der Waals Interactions
journal, April 2014


A tractable and accurate electronic structure method for static correlations: The perfect hextuples model
journal, July 2010


Effects of electron repulsion in conjugated hydrocarbon diradicals
journal, June 1977


Synthesis and characterization of phenalenyl cations, radicals, and anions having donor and acceptor substituents: three redox states of modified odd alternant systems
journal, December 1989


Hexathiophenalenylium Cations: Syntheses, Structures, and Redox Chemistry
journal, March 2013


Cyclo-biphenalenyl Biradicaloid Molecular Materials: Conformation, Tautomerization, Magnetism, and Thermochromism
journal, February 2011


A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010


Van der Waals density functionals applied to solids
journal, May 2011


Preparation and interconversion of dithiatriazine derivatives: crystal, molecular, and electronic structure of bis(5-phenyl-1,3,2,4,6-dithiatriazine) (PhCN3S2)2
journal, December 1985


The structures and stabilities of singlet and triplet dithiatriazines: a computational study
journal, September 1988


Chiral Stable Phenalenyl Radical: Synthesis, Electronic-Spin Structure, and Optical Properties of [4]Helicene-Structured Diazaphenalenyl
journal, May 2012


Dual Association Modes of the 2,5,8-Tris(pentafluorophenyl)phenalenyl Radical
journal, May 2014


Playing with organic radicals as building blocks for functional molecular materials
journal, January 2012


Works referencing / citing this record:

Effect of Substitution on the Hysteretic Phase Transition in a Bistable Phenalenyl‐Based Neutral Radical Molecular Conductor
journal, February 2019


Synthesis, Characterization, and Functionalization of 1‐Boraphenalenes
journal, July 2018


Constructing Stable π-Dimers: Two Parallel Pancake π-π Bonds
journal, October 2018


Origin of Bistability in the Butyl-Substituted Spirobiphenalenyl-Based Neutral Radical Material
journal, May 2017


Pancake Bonding: An Unusual Pi-Stacking Interaction
journal, November 2018


Synthesis, Characterization, and Functionalization of 1-Boraphenalenes
journal, June 2018