skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

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

Journal Article · · Journal of Physical Chemistry Letters
 [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)
+ Show Author Affiliations

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.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC05-00OR22725
OSTI ID:
1185694
Journal Information:
Journal of Physical Chemistry Letters, Vol. 6, Issue 12; ISSN 1948-7185
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 28 works
Citation information provided by
Web of Science

References (41)

Synthetic organic spin chemistry for structurally well-defined open-shell graphene fragments journal February 2011
Design of organic metals and superconductors journal July 1975
Quantum chemical studies in the design of organic metals. III. Odd-alternant hydrocarbons - The phenalenyl (ply) system journal January 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
Exceptionally Long (≥2.9 Å) C−C Bonds between [TCNE]− Ions: Two-Electron, Four-Center π*-π* C−C Bonding in π-[TCNE]22− journal July 2001
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
Pancake bonds: π-Stacked dimers of organic and light-atom radicals journal September 2014
Four-Center Carbon−Carbon Bonding † journal March 2007
Magneto-Opto-Electronic Bistability in a Phenalenyl-Based Neutral Radical journal May 2002
Resonating Valence-Bond Ground State in a Phenalenyl-Based Neutral Radical Conductor journal July 2005
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
Intermolecular π-to-π Bonding between Stacked Aromatic Dyads. Experimental and Theoretical Binding Energies and Near-IR Optical Transitions for Phenalenyl Radical/Radical versus Radical/Cation Dimerizations journal October 2004
Intermolecular Covalent π−π Bonding Interaction Indicated by Bond Distances, Energy Bands, and Magnetism in Biphenalenyl Biradicaloid Molecular Crystal journal February 2007
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
Extended multi-configuration quasi-degenerate perturbation theory: The new approach to multi-state multi-reference perturbation theory journal June 2011
The calculation of small molecular interactions by the differences of separate total energies. Some procedures with reduced errors journal October 1970
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

Cited By (7)

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
Tuning the Chemical Hardness of Boron Nitride Nanosheets by Doping Carbon for Enhanced Adsorption Capacity journal September 2017

Similar Records

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY