Related Experiment Video
Updated: May 28, 2026

Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks
Published on: June 9, 2023
Electron localization function study on intramolecular electron transfer in the QTTFQ and DBTTFI radical anions
Jaroslaw Kalinowski1, Slawomir Berski, Agnieszka J Gordon
1Laboratory of Physical Chemistry, Department of Chemistry, University of Helsinki, Helsinki, Finland.
Abstract:
The unsymmetrical distribution of the unpaired electron in the ground state of the DBTTFI(•-) radical anion (bi(6-n-butyl-5,7-dioxo-6,7-dihydro-5H-[1,3]dithiolo[4,5-f]isoindole-2-ylidene) is theoretically predicted using the M06-2X/6-31+G(d,p) level of calculations. The results are additionally confirmed by single point calculations at B3LYP/aug-cc-pVTZ, LC-ωPBE/aug-cc-pVTZ, and M06-2X/aug-cc-pVTZ levels. DBTTFI, containing the TTF (tetrathiafulvalene) fragment, may be used in the construction of organic microelectronic devices, similarly to the radical anion of QTTFQ. The unsymmetrical distribution of spin density in (QTTFQ)(•-) has been confirmed using M06-2X/aug-cc-pVTZ calculations, with subsequent study using topological analysis of electron localization function (ELF). The reorganization of the chemical bonds during intramolecular electron transfer in (QTTFQ)(•-) and (DBTTFI)(•-) has been analyzed using bonding evolution theory (BET). The reaction path has been simulated by the IRC procedure, and the evolution of valence basins has been described using catastrophe theory. The simple mechanisms: (QTTFQ)(•-): η-1-3-CC(+)-0: (-•)(QTTFQ) and (DBTTFI)(•-): η-1-3-[F](4)[F(+)](4)-0: (-•)(DBTTFI), each consisting of three steps, have been observed. Two cusp or 4-fold catastrophes occur immediately after the TS. Our study shows that potential future microelectronic devices, constructed on the basis of the (QTTFQ)(•-) and (DBTTFI)(•-) systems, should exploit the properties of the C═C bond.
More Related Videos
08:54Vibrational Spectra of a N719-Chromophore/Titania Interface from Empirical-Potential Molecular-Dynamics Simulation, Solvated by a Room Temperature Ionic Liquid
Published on: January 25, 2020
08:22Measurement of Ultrafast Vibrational Coherences in Polyatomic Radical Cations with Strong-Field Adiabatic Ionization
Published on: August 6, 2018
Related Concept Videos
Electron Paramagnetic Resonance (EPR) Spectroscopy: Organic Radicals
Radical Reactivity: Overview
Radicals: Electronic Structure and Geometry
Accordingly, the structure of a trivalent radical lies between the geometries of carbocations and carbanions. An sp2-hybridized carbocation is trigonal planar, while an sp3-hybridized carbanion is trigonal pyramidal. Here, the difference in geometry is...
Radical Reactivity: Intramolecular vs Intermolecular
Radical Reactivity: Nucleophilic Radicals
Radical Formation: Abstraction
Even though homolysis produces radicals, it is different from radical...