Donor-Substituted 1,1,4,4-Tetracyanobutadienes (TCBDs): New Chromophores with Efficient Intramolecular Charge-Transfer Interactions by Atom-Economic Synthesis

• Published in: Chemistry : a European journal Vol. 12; no. 7; pp. 1889 - 1905
• Main Authors: Michinobu, Tsuyoshi, Boudon, Corinne, Gisselbrecht, Jean-Paul, Seiler, Paul, Frank, Brian, Moonen, Nicolle N. P., Gross, Maurice, Diederich, François
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 20-02-2006; WILEY‐VCH Verlag
• Subjects: charge transfer; conjugation; cycloaddition; donor-acceptor systems; electrochemistry
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.200501113

A wide variety of monomeric and oligomeric, donor‐substituted 1,1,4,4‐tetracyanobutadienes (TCBDs) have been synthesized by [2+2] cycloaddition between tetracyanoethylene (TNCE) and donor‐substituted alkynes, followed by electrocyclic ring opening of the initially formed cyclobutenes. Reaction yields are often nearly quantitative but can be affected by the electron‐donating power and steric demands of the alkyne substituents. The intramolecular charge‐transfer (CT) interactions between the donor and TCBD acceptor moieties were comprehensively investigated by X‐ray crystallography, electrochemistry, UV‐visible spectroscopy, and theoretical calculations. Despite the nonplanarity of the new chromophores, which have a substantial twist between the two dicyanovinyl planes, efficient intramolecular CT interactions are observed, and the crystal structures demonstrate a high quinoid character in strong donor substituents, such as N,N‐dimethylanilino (DMA) rings. The maxima of the CT bands shift bathochromically upon reduction of the amount of conjugative coupling between strong donor and acceptor moieties. Each TCBD moiety undergoes two reversible, one‐electron reduction steps. Thus, a tri‐TCBD derivative with a 1,3,5‐trisubstituted benzene core shows six reversible reduction steps within an exceptionally narrow potential range of 1.0 V. The first reduction potential Ered,1 is strongly influenced by the donor substitution: introduction of more donor moieties causes an increasingly twisted TCBD structure, a fact that results in the elevation of the LUMO level and, consequently, a more difficult first reduction. The potentials are also strongly influenced by the nature of the donor residues and the extent of donor–acceptor coupling. A careful comparison of electrochemical data and the correlation with UV‐visible spectra made it possible to estimate unknown physical parameters such as the Ered,1 of unsubstituted TCBD (−0.31 V vs Fc+/Fc) as well as the maxima of highly broadened CT bands. Donor‐substituted TCBDs are stable molecules and can be sublimed without decomposition. With their high third‐order optical nonlinearities, as revealed in preliminary measurements, they should become interesting chromophores for ultra‐thin film formation by vapor deposition techniques and have applications in opto‐electronic devices.
Atom economy! An extensive series of donor‐substituted tetracyanobutadienes (TCBDs, two examples of which are shown here) has been prepared by short, atom‐economic synthesis. Despite their twisted structures, efficient donor–acceptor π‐electron conjugation in these novel chromophores was demonstrated by a variety of methods, including X‐ray crystallography, UV‐visible spectroscopy (depicted), and electrochemistry.