Structural characterization of 2,3,5,6-tetramethyl-p-phenylenediamine radical cation and its dimer in molecular crystals

[Display omitted] •We reported the crystal structures of two reaction products between DDA and bromanile.•X-ray crystal analyses showed that these are 1:1 CT complexes and bromide salts.•The electronic structures of DDA complexes were investigated by UPS, and the results were discussed with the DFT...

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Bibliographic Details
Published in:Journal of molecular structure 2015-03, Vol.1083, p.260-267
Main Authors: Takaiwa, Tsukasa, Koyama, Atsushi, Nagaishi, Yoshihide, Nakajima, Kiyohiko, Sumimoto, Michinori, Hori, Kenji, Matsuzaki, Susumu, Fujimoto, Hitoshi
Format: Article
Language:English
Subjects:
Acceptors (electronic)
Anions
Cations
Charge-transfer complex
Crystal structure
Crystallization
Electronic structure
Halides
Mathematical analysis
Molecular structure
Ultraviolet photoelectron spectroscopy
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Summary:[Display omitted] •We reported the crystal structures of two reaction products between DDA and bromanile.•X-ray crystal analyses showed that these are 1:1 CT complexes and bromide salts.•The electronic structures of DDA complexes were investigated by UPS, and the results were discussed with the DFT calculations.•The degree of charge-transfer was estimated to be about 0.7 for the CT complex. Reaction between 2,3,5,6-tetramethyl-p-phenylenediamine (DDA) and bromanil (BA) gave two different crystalline products, needle-like and block-shaped crystals. The former was an alternate-stack 1:1 charge-transfer complex between DDA and BA with an electron-transfer ratio of about 0.7. The latter was a bromide salt of DDA, which was crystallized simultaneously with the decomposition of BA anions. The DDA molecules in the salt were dimerized even at room temperature. The similar products were obtained by a reaction between DDA and chloranil. The molecular and electronic structures are discussed with the calculation results of the density functional theory. This report has two additional meanings on the synthesis of charge-transfer complexes with using haloanils, which are commonly used as electron acceptors: (1) special attention must be paid for contaminating halide ions in characterizing reaction products and in discussing their properties, and (2) a new moderate synthetic root of halide complexes becomes available when using haloanils.
ISSN:0022-2860
1872-8014
DOI:10.1016/j.molstruc.2014.12.005