SOLID COMPLEXES OF THE Pi-AMPHOTERIC MOLECULE p-TRICYANOVINYL-N,N-DIMETHYLANILINE.

Article abstract of DOI:10.1080/00268948008072422

Solid pi-complexes of p-tricyanovinyl-N,N-dimethylaniline (TCVDMA) were isolated for the first time. The complexing molecules include the simple aromatic solvents benzene, toluene, chlorobenzene, 1,2,4-trichlorobenzene, and N,N-dimethylaniline (DMA), 2,4,7-trinitrofluorenone (TNF), and p-chloranil. Lattice constants are reported for the five complexes with aromatic solvents and TNF. The complexes of TCVDMA with benzene, toluene, and chlorobenzene have the stoichiometry 2TCVDMA (aromatic) and similar lattice constants. The complexes of TCVDMA with DMA and 1,2,4-trichlorobenzene have the unusual stoichiometry 4TCVDMA (aromatic) with similar lattice constants including a short unit cell dimension of ca. 4. 0 A. The complexes with DMA, TNF, and p-chloranil are found to have new absorption assigned to charge-transfer transitions and are thus Mulliken donor-acceptor complexes. Based on molecular energy levels and redox potentials, TCVDMA behaves as a donor in its complexes with TNF and p-chloranil and as an acceptor in its complex with DMA. Thus TCVDMA is the first example of a molecule to yield well-defined solid complexes in which it behaves as a donor with one molecule and as an acceptor with another. While TCVDMA has long been known to be a solvatochromic, its solvent shifts do not give good correlations with E//T* and Z. The most quantitative correlation found was between the frequency shift and a refractive index function for the solvents benzene, toluene, and chlorobenzene. The sensitivity of the spectra of solid evaporated films of TCVDMA to degree of crystallinity thermal history, and exposure to benzene vapor is reported. A recent claim that p-dimethylaminobenzylidenemalononitrile, a moleculel similar in structure to TCVDMA, gave different crystalline forms on crystallization from benzene and methanol was found not to be reproducible.

Full text of DOI:10.1080/00268948008072422

This article was downloaded by: [University of Waterloo]
On: 15 December 2014, At: 11:20
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954
Registered office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH,
UK
Molecular Crystals and Liquid
Crystals
Publication details, including instructions for
authors and subscription information:
http://www.tandfonline.com/loi/gmcl16
Solid Complexes of the
Pi-Amphoteric Molecule
p-Tricyanovinyl-N, N-
Dimethylaniline
D. J. Sandman a b , A. F. Richter c , D. E. Warner a d
& G. T. Fekete a
a Xerox Corporation , Joseph C. Wilson Center for
Technology , Xerox Square, W-114, Rochester, New
York, 14644, U.S.A.
b GTE Laboratories, Inc. , Advance Technology
Laboratory , 40 Sylvan Road, Waltham, MA 02154
c Co-operative Education Student , Drexel
University , 1978–79
d Co-operative Education Student , Rochester
Institute of Technology , 1978–79
Published online: 20 Apr 2011.
To cite this article: D. J. Sandman , A. F. Richter , D. E. Warner & G. T. Fekete
(1980) Solid Complexes of the Pi-Amphoteric Molecule p-Tricyanovinyl-N, N-
Dimethylaniline, Molecular Crystals and Liquid Crystals, 60:1-2, 21-35, DOI:
10.1080/00268948008072422
To link to this article: http://dx.doi.org/10.1080/00268948008072422
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the
information (the “Content”) contained in the publications on our platform.
However, Taylor & Francis, our agents, and our licensors make no

representations or warranties whatsoever as to the accuracy, completeness,
or suitability for any purpose of the Content. Any opinions and views
expressed in this publication are the opinions and views of the authors, and
are not the views of or endorsed by Taylor & Francis. The accuracy of the
Content should not be relied upon and should be independently verified with
primary sources of information. Taylor and Francis shall not be liable for any
losses, actions, claims, proceedings, demands, costs, expenses, damages,
and other liabilities whatsoever or howsoever caused arising directly or
indirectly in connection with, in relation to or arising out of the use of the
Content.
This article may be used for research, teaching, and private study purposes.
Any substantial or systematic reproduction, redistribution, reselling, loan,
sub-licensing, systematic supply, or distribution in any form to anyone is
expressly forbidden. Terms & Conditions of access and use can be found at
http://www.tandfonline.com/page/terms-and-conditions