NDLI: Direct Observation of Mixed-Valence and Radical Cation Dimer States of Tetrathiafulvalene in Solution at Room Temperature: Association and Dissociation of Molecular Clip Dimers Under Oxidative Control

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Direct Observation of Mixed-Valence and Radical Cation Dimer States of Tetrathiafulvalene in Solution at Room Temperature: Association and Dissociation of Molecular Clip Dimers Under Oxidative Control

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Direct Observation of Mixed-Valence and Radical Cation Dimer States of Tetrathiafulvalene in Solution at Room Temperature: Association and Dissociation of Molecular Clip Dimers Under Oxidative Control

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Chen, Nai-chia Lai, Chien-chen Chiu, Sheng-hsien Chiang, Pinn-tsong
Description	Author Affiliation: Chiang PT ( Department of Chemistry, National Taiwan University, Taipei, Taiwan ROC.)
Abstract	We have observed the mixed-valence and radical cation dimer states of a glycoluril-based molecular clip with tetrathiafulvalene (TTF) sidewalls at low concentration (1 mM) at room temperature. This molecular clip has four consecutive anodic steps in its cyclic voltammogram, which suggests a sequential oxidation of these TTF sidewalls to generate species existing in several distinct charge states: neutral monomers, mixed-valence dimers, radical cation dimers, and fully oxidized tetracationic monomers. The observation of characteristic NIR spectroscopic absorption bands at approximately 1650 and 830 nm in spectroelectrochemistry experiments supports the presence of intermediary mixed-valence and radical cation dimers, respectively, during the oxidation process. The stacking of four TTF radical cations in the dimer led to the appearance of a charge-transfer band at approximately 946 nm. Nanoelectrospray ionization mass spectrometry was used to verify the tricationic state and confirm the existence of other different charged dimers during the oxidation of the molecular clip.
ISSN	09476539
e-ISSN	15213765
Journal	Chemistry - A European Journal
Issue Number	21
Volume Number	14
Language	English
Publisher	Wiley-VCH;ChemPubSoc Europe
Publisher Date	2008-01-01
Publisher Place	Germany
Access Restriction	Open
Subject Keyword	Heterocyclic Compounds Chemistry Dimerization Electrochemistry Nanotechnology Oxidation-Reduction Spectrometry, Mass, Electrospray Ionization Temperature Research Support, Non-U.S. Gov't
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry Catalysis

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