Distorted Molecules: Perturbation Design, Preparation and Structures

The structure of a molecule can change considerably as its energy and thus its electron distribution within the time-domain of dynamic relaxation varies. Based on comparison of approriate measured data of related compounds and supported by quantum chemical calculations, therefore, charge-perturbed and/or sterically overcrowded molecules can be designed. Their preparation, handling, and structural characterization, frequently under extreme and especially largely aprotic conditions, provides some surprises. New structural principles become evident and old-fashioned ones are confirmed. Thus the contact-ion aggregates that form on ultrasonically supported reduction of unsaturated hydrocarbons with sodium metal partly contain dibenzene sodium sandwiches. Vicinal dimethylamino substituents or isoelectronic isopropyl groups cause steric overcrowding and facilitate oxidation to molecular cations by energetically favorable delocalization of the generated positive charge. Molecules and molecular ions in which an even number of π electrons are distributed over a σ skeleton containing an odd number of centers preferentially form cyanine subunits. This is demonstrated by the novel ethene dication and dianion salts with central CC single bonds and molecular halves twisted relative to each other. Altogether in two years well over 50 structures have been determined. Much has been learned from them, especially about electron transfer and contact ion-pair formation in aprotic solvents. Nevertheless, we had to realize that answers to many questions, above all “what crystallizes, how, and why”, are still out of reach.