RESUMEN
Hexaarylbenzene (HAB) derivatives are versatile aromatic systems playing a significant role as chromophores, liquid crystalline materials, molecular receptors, molecular-scale devices, organic light-emitting diodes and candidates for organic electronics. Statistical synthesis of simple symmetrical HABs is known via cyclotrimerization or Diels-Alder reactions. By contrast, the synthesis of more complex, asymmetrical systems, and without involvement of statistical steps, remains an unsolved problem. Here we present a generally applicable synthetic strategy to access asymmetrical HAB via an atom-economical and high-yielding metal-free four-step domino reaction using nitrostyrenes and α,α-dicyanoolefins as easily available starting materials. Resulting domino product-functionalized triarylbenzene (TAB)-can be used as a key starting compound to furnish asymmetrically substituted hexaarylbenzenes in high overall yield and without involvement of statistical steps. This straightforward domino process represents a distinct approach to create diverse and still unexplored HAB scaffolds, containing six different aromatic rings around central benzene core.
RESUMEN
Mixed cyclotrimerization reactions of diarylacetylenes (tolans) were applied to generate a library of multiple porphyrin-hexaphenylbenzene (HPB) architectures. Successful reactions, which could be influenced by the ratio of tolan starting materials, were conducted using dicobaltoctacarbonyl as a catalyst. Separation of the reaction products was performed by chromatographic and crystallization techniques. The physical properties were investigated with respect to the number of porphyrins per HPB and their substitution pattern.
