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Experimental and DFT Studies of the Electron-Withdrawing Ability of Perfluoroalkyl (RF) Groups: Electron Affinities of PAH(RF)n Increase Significantly with Increasing R F Chain Length

Journal Article · · Chemistry - A European Journal
 [1];  [2];  [2];  [3];  [1];  [2];  [3];  [4];  [1];  [1]
  1. Department of Chemistry, Colorado State University, Fort Collins Colorado 80523 USA
  2. Department of Chemistry, University at Albany, State University of New York, Albany New York 12222 USA
  3. Physical Sciences Division, Pacific Northwest National Laboratory, MS K8 88, P.O. Box 999 Richland Washington 99352 USA
  4. Department of Electrochemistry and Conducting Polymers, Liebniz Institute for Solid State and Materials Research, Dresden 01069 Germany
+ Show Author Affiliations

Two series of aromatic compounds with perfluoroalkyl (RF) groups of increasing length, 1,3,5,7-naphthalene(RF)4 and 1,3,5,7,9-corannulene(RF)5, have been prepared and their electronic properties studied by low-temperature PES (i.e., gas-phase electron affinity (EA) measurements). These and many related compounds were also studied by DFT calculations. The data demonstrate unambiguously that the electron-withdrawing ability of RF substituents increases significantly and uniformly from CF3 to C2F5 to n-C3F7 to n-C4F9.

Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Organization:
USDOE
DOE Contract Number:
AC05-76RL01830
OSTI ID:
1439682
Report Number(s):
PNNL-SA-129788; 50069; KC0301050
Journal Information:
Chemistry - A European Journal, Journal Name: Chemistry - A European Journal Journal Issue: 6 Vol. 24; ISSN 0947-6539
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English

References (52)

A thermophysical and structural characterization of ionic liquids with alkyl and perfluoroalkyl side chains journal January 2015
Perfluoroalkylfullerenes journal August 2014
Synthesis of perfluoroalkylated pentacenes and evaluation of their fundamental physical properties journal January 2017
Gas-Phase Acidity of Polyfluorinated Hydrocarbons. Effects of Fluorine and the Perfluoroalkyl Group on Acidity journal July 2014
Solubilization of n-alkylbenzene and n-perfluoroalkylbenzene in hydrogenated and fluorinated surfactants micelles journal May 2009
Minimally augmented Karlsruhe basis sets journal December 2010
Mass Spectrometry and Photoelectron Spectroscopy of Tetracene Cluster Anions, (Tetracene) ( n = 1−100):  Evidence for the Highly Localized Nature of Polarization in a Cluster Analogue of Oligoacene Crystals journal October 2007
Medicinal applications of perfluoroalkylated chain-containing compounds journal June 2014
Linear Bis(perfluoroalkyl) Complexes of Nickel Bipyridine journal November 2011
Relationship between Electron Affinity and Half-Wave Reduction Potential: A Theoretical Study on Cyclic Electron-Acceptor Compounds journal September 2016
Partitioning Solvophobic and Dispersion Forces in Alkyl and Perfluoroalkyl Cohesion journal November 2014
Incremental Tuning Up of Fluorous Phenazine Acceptors journal January 2016
Taming Hot CF 3 Radicals: Incrementally Tuned Families of Polyarene Electron Acceptors for Air-Stable Molecular Optoelectronics journal March 2013
Metal carbonyl-phosphorus trifluoride systems. XIII. Fluorine nuclear magnetic resonance studies on RfCo(PF3)x(CO)4-x compounds (Rf = trifluoromethyl, pentafluoroethyl, heptafluoropropyl) journal April 1976
Electrochemical, Spectroscopic, and DFT Study of C 60 (CF 3 ) n Frontier Orbitals ( n = 2−18):  The Link between Double Bonds in Pentagons and Reduction Potentials journal September 2007
Taming Hot CF 3 Radicals: Incrementally Tuned Families of Polyarene Electron Acceptors for Air-Stable Molecular Optoelectronics journal March 2013
Perspective on Fluorocarbon Chemistry journal January 2004
Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy journal January 2005
Electron affinities of some polycyclic aromatic hydrocarbons, obtained from electron-transfer equilibria journal August 1993
C 20 H 4 (C 4 F 8 ) 3 : A Fluorine-Containing Annulated Corannulene that Is a Better Electron Acceptor Than C 60 journal June 2013
Development of novel synthetic routes to bis(perfluoroalkyl)-substituted anthracene derivatives journal January 2013
Fast evaluation of density functional exchange-correlation terms using the expansion of the electron density in auxiliary basis sets journal December 1997
A Buckybowl with a Lot of Potential: C5-C20H5(CF3)5 journal April 2012
Perfluoroalkyl and -aryl Zinc Ate Complexes: Generation, Reactivity, and Synthetic Application journal June 2015
Partitioning Solvophobic and Dispersion Forces in Alkyl and Perfluoroalkyl Cohesion journal November 2014
Perfluoroalkylation of Square-Planar Transition Metal Complexes: A Strategy To Assemble Them into Solid State Materials with a π–π Stacked Lamellar Structure journal March 2016
Gas-phase acidity of bis[(perfluoroalkyl)sulfonyl]imides. Effects of the perfluoroalkyl group on the acidity: GAS-PHASE ACIDITY OF BIS[(PERFLUOROALKYL)SULFONYL]IMIDES journal May 2014
Steering Power of Perfluoroalkyl Substituents in Crystal Engineering: Tuning the π–π Distance While Maintaining the Lamellar Packing Motif for Aromatics with Various Sizes of π-Conjugation journal March 2015
The effect of fluorination (2): dependence of alkyl chain length on the crystal structures of mesogenic alkyl 4-[2-(perfluorohexyl)ethoxy]benzoates journal March 2011
Substituent effects in a series of 1,7-C60(RF)2 compounds (RF = CF3, C2F5, n-C3F7, i-C3F7, n-C4F9, s-C4F9, n-C8F17): electron affinities, reduction potentials and E(LUMO) values are not always correlated journal January 2012
PRIRODA-04: a quantum-chemical program suite. New possibilities in the study of molecular systems with the application of parallel computing journal March 2005
Perfluoroalkyl Cobalt(III) Fluoride and Bis(perfluoroalkyl) Complexes: Catalytic Fluorination and Selective Difluorocarbene Formation journal December 2015
Generalized Gradient Approximation Made Simple journal October 1996
Copper Causes Regiospecific Formation of C 4 F 8 -Containing Six-Membered Rings and their Defluorination/Aromatization to C 4 F 4 -Containing Rings in Triphenylene/1,4-C 4 F 8 I 2 Reactions journal December 2015
A Buckybowl with a Lot of Potential: C5-C20H5(CF3)5 journal April 2012
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu journal April 2010
Some Relations between Reaction Rates and Equilibrium Constants. journal August 1935
Electronic Properties of Trifluoromethylated Corannulenes journal October 2012
Toward a Physical Interpretation of Substituent Effects: The Case of Fluorine and Trifluoromethyl Groups journal July 2014
Trifluoromethyl/Perfluoroalkyl Corannulenes: Directed Synthesis and Photophysical Characterization: Trifluoromethyl/Perfluoroalkyl Corannulenes: Directed Synthesis and Photophysical Characterization journal January 2017
Corannulene Molecular Rotor with Flexible Perfluorobenzyl Blades: Synthesis, Structure and Properties journal May 2015
A survey of Hammett substituent constants and resonance and field parameters journal March 1991
Bismuth Perfluoroalkylphosphinates: New Catalysts for Application in Organic Syntheses journal December 2016
Elektronische Eigenschaften trifluormethylierter Corannulene journal October 2012
Arene Trifluoromethylation: An Effective Strategy to Obtain Air-Stable n-Type Organic Semiconductors with Tunable Optoelectronic and Electron Transfer Properties journal July 2012
C 20 H 4 (C 4 F 8 ) 3 : A Fluorine-Containing Annulated Corannulene that Is a Better Electron Acceptor Than C 60 journal June 2013
Poly(trifluoromethyl)azulenes: structures and acceptor properties journal January 2014
The ORCA program system: The ORCA program system journal June 2011
Single-Step Gas-Phase Polyperfluoroalkylation of Naphthalene Leads to Thermodynamic Products journal March 2014
Experimental and computational analysis of supramolecular motifs involving C sp2 (aromatic)–F and CF 3 groups in organic solids journal January 2016
Core Perylene Diimide Designs via Direct Bay- and ortho -(Poly)trifluoromethylation: Synthesis, Isolation, X-ray Structures, Optical and Electronic Properties : Core Perylene Diimide Designs journal September 2015
Perfluorinated gelators for solidifying fluorous solvents: effects of chain length and molecular chirality journal January 2015

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Environmental Molecular Sciences Laboratory